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r-=i f 



ANNUAL REPORT 

ON ESSENTIAL OILS 
SYNTHETIC PERFUMES 

PUBLISHED BY 

SGHIMMEL ^ CO. 

MILTITZ, NEAR LEIPZIG 



EDITION 1922. 



Sole Agents in the United States and Canada 
FRITZSCHE BROTHERS, INC. 

32^ BEEKMAN STREET, MEW YORK CITY. 



*5I'; .•'.;•»' -•.-:• " 



K 






-• >• 



||: Contents. 



r,fv' 



< 



•y 









t 



1 



Page 

^ „ ^ Commercial Notes and Scientific Information on Essential Oils 5 

$!^\ Pharmacopoeias 85 

Chemical Preparations and Drugs . 90 

pi?^ J Notes on Scientific Research Work in the Domain of Terpenes and Essential Oils. 

General 103 

Bibliography 108 

Analytical 110 

I Physical . 115 

Botanical 118 

Phy to-physiological .121 

Pharmaco-physiological 122 

Chemical 130 

Hydrocarbons 130 

Alcohols .' 138 

Aldehydes 143 

Ketones 146 

Phenols and Phenol Ethers . . . % 150 

Acids, EsterS) and Lactones 152 

Glucosides 154 

Nitrogenous Bodies 155 



List of abbreviations, 
d = specific gravity, 

djoo = specific gravity at 20° (in references from our laboratories uniformly compared 

with water at 15°). 
d^ '= specific gravity at 20°, compared with water at 4°; 
<<D»o = optical rotation at 20°, in a 100 mm. tube. 
Wd = specific rotation. 
nD»o = index of refraction at 20° 
sol. p. = solidifying point, 
m. p. = melting point, 
b. p. = boiling point. 

n = normal. I 

acet. =^ acetylation. ! 

acid v. = acid value; ester v. = ester value; sap. v. = saponification value. .'i 

g. = gram; cc. = cubic centimeter; mm. = millimeter. 'i 



Temperatures are uniformly given in degrees Centigrade. 
The strength of alcohol, if not otherwise indicated, is given in per cent, by volume. 



i 



Commercial and sciEWTinc notes on essential oils. 



\ 



Commercial Notes and Scientific Information 

on Essential Oils. 

oil of Abies PIndrow. — Cones, and ^oung shoots of the Indian silver fir, Ahks 
Pindrmv (Royle) Spach*), yielded on steam distillatioji an oil, of which we received 
a sample some time ago. It was colourless, of agreeable balmy odour and showed 
the following constants:— diBo 0.8647, «d — 10^59', nptoo 1.47328, acid v.^0.3, ester v. 
6.5 = 2.3 per cent, ester (bornyl acetate), soluble with slight turbidity in 3 volumes and 
more of 90 per cent, alcohol; soluble in 1 vol. and more of 95 per cent, alcohol. 

The tree occurs in the lower Himalaya regions, at a height of between 2400 and 
3000 metres. 

Oil of Aburachan. — By. distillation of the leaves and twigs of Lindera prascox, Bl., 
a lauracea growing in Japan, Y. Shinosaki') obtained about 0.3 per pent, of a light 
brown coloured oil which had a somewhat strongly camphoraceous odeur and the 
following characters : — di6o 0.9094 to 0.9178; « — 3^57' to — 5^1'; Hmoo 1.4850 to 1.4866; 
acid value, 0.69 to 0.92; sap. value, 45.76 to 48.69; sap. val. after acetylation, 90.48 to 
98'.62i The following substances were isolated*): — 2 per cent, of a-pinene, 14 per cent 
of camphene, 8 per cent, of cineole, 10 per cent, of an aliphatic terpene (b. p. 40 to 41° 
at 2 mm., diso 0.8251 , nptoo 1 .4840), bomeol present in the oil partly free and partly as 
ester, geraniol (23 per cent, with borneol), 8 per cent, of caryophyllene, 21 per cent, of 
f^cadinene, 5 per cent, of a sesquiterpene alcohol CiftHseO, and a tertiary alcohol (b. p. 
140 to 1420at4mm.'; di5o 0.9740; « — 5° noioo 1 .5072). From the alkaline liquor after 
saponification of the original oil there were isolated: — acetic acid, a decylenic acid 
CioHisOa (b. p. 106 to 1070 at 1.5 mm., duo 0.9339, noioo 1.4552, acid value 328 to 334.9, 
iodine value 142.24, probably identical with citronellic acid) and a saturated weak acid 
of higher series and having a high boiling point. 

Af owan Oil. — Y. Murayama found in this oil a new terpene, moslene (cf . p. 51 
of this Report), 

Almond Oil, bitter. — A bitter almond oil "genuine, free from chlorine", sent us 
for inspection, proved an "excellent" acquisition for the buyer, as it was a crude, 
strongly chlorinated benzaldehyde of a reddish-brown colour (due to iron), containing 
about 30 p^er cent, of nitrobenzene. 

The defects of the product were revealed at once by its constants, as it was far 
too heavy (diso 1.1237), had too high a refraction (nDao 1.54876) and did not dissolve 
in 50 per cent, alcohol; besides, it gave a strong chlorine reaction. It resulted on closer 
investigation that these irregularities were due to nitrobenzene, present in the proportion 



>) According to Brandis, this is only a variety of Abies Webltianay Lindley. Comp. A. Engler and K. Prantl, 
Die tifitUrUchen Fflanzenfamilien vol. II, 1, page 60. -- •) Joum. chem. Ind. Japah 24 (1921), 444. According to 
Joum. Soc. chem. Ind. 40 (1921), A. 674. — •) Details are missing in the abstract. 



« - 



6 Report of Schimmei- S Co. 1922. 

indicated above. After having isolated it, it could be identified by its odour and its 
other properties:— di5o 1.2032, noao 1.55104, solidification point +3.6°. 

Nitrobenzene being highly poisonous, as we have repeatedly pointed out in our 
JR^ports^)^ its use as an adulterant is inexcusable. We can only take it that the setter 
was too silly to understand the bearing of his action, otherwise he ought to have 
realized what ill effects the addition of nitrobenzene to a product often used in the 
household may have. 

As E. Pinoff *) says, the presence of nitrobenzene in bitter almond oil can easily 
bfc proved in the following way:— 10 cc. of a 40 per cent, formaldehyde solution and 
20 cc. of concentrated ammonia are filled in a cylinder holding 100 cc. and which can 
be closed with a stopper of indiarrubber. ' After having shaken the mixture carefully 
for some time, it must be allowed to stand for five minutes. Then it is shaken 
vigorously with 10 cc. of the bitter almond oil and again allowed to stand. The pure 
bitter almond forms an emulsion with the , formaldehyde-ammonia, whereas the nitro- 
benzene deposits as a clear liquid. The nitrobenzene is then reduced with zinc and 
hydrochloric acid to aniline, which can be identified by one of the well-known reactions. 

We are of opinion that the usual method, according to which the benzaldehyde is 
bound to bisulphite, is simpler and more convenient (cf, Gildemeister and Hoffmann, 
The Volatile OUs, 2"^ edition, vol. I, p. 585). 

Oil of Amoinis jamaicensis. — The oil of Amomis jamakensis (wild pimento), the 
constants of which we quoted in our Report of 1020, p. 6 after a communication 
in the Bulletin of the Imperial Institute, London, has been further investigated by 
O. D. Roberts^). After removing the free acids (0.2 per cent, acetic and caproic acids), 
an aldehyde (0.1 per cent.) and a phenol (0.1 per cent., not eugenol) the oil was Hydro- 
lysed with boiling alcoholic potassium hydroxide and the oil separating after addition 
of water and extracting with ether was submitted to fractional distillation at 14 mm. 
pressure, which gave the following fractions:— l.B. p. 75 to 80° (175 to 190 ^ at ordinary 
pressure), 32 per cent, of the original oil ; ?. b. p. 80 to 95° (190 to 205° ord. pr.), 42 per cent.; 
3. b. p. 95 to 1 10° (205 to 220°, ord. pr.), 4 per cent.; 4. b. p. 1 10 to 125° (220 to 235° ord. 
pr.), 6 per cent; residue 16 per cent, of the original oil. Fraction 1 contained 47 per cent, 
cineole = 15 per cent, of the original oil (resorcinol method and iodole addition com- 
pound), a-phellandrene (nitrite, m. p. 1 12 to 1 13°), and dipentene (tetrabromide, m. p. 124 o). 
The principal part of fraction 2 had the constants : — b. p. 197 to 1 98°, djg 0.8693, ac— 3°39', 
nojoo 1.4655 and was identical with Minalool (oxidation to citral; a-citryl-/?-naphthocin- 
choninic acid, m. p. 200°). In fraction 4 geraniol was proved tob^ present (diphenyl- 
urethahe, m. p. 80 to 81°). The residue boiling above 235° was heated on the water 
bath under reduced pressure for some weeks with sodium. There was thus dbtained 
by distillation under 15 mm. pressure a colourless oil, with a slight balsamic odour, 
b. p. 245 to 290O (uncorr.), dJU 0.9320, which was still slowly attacked by sodium. 

The author summarizes his investigation as follows: — The oil of Amomis jamaicensis 
contains about 17 per cent, of terpenes (<x-phellandrene and dipentene), 15 percent, of 
cineole, 38.3 per cent, of alcohols (chiefly Minalool with some geraniol), 1.5 per cent, 
of ester (linalyl acetate), each 0.1 per cent, of phenols and aldehydes, both undetermined, 
0.2 per cent. of. acetic and caproic acids, and 27.8 per cent, residue probably containing 
sesquiterpenes. 



*) Cf. for instance Beport 1918, 5. — «) Pharm. Zentralh. 02 (t92I), 610. — «) Journ, Soc, chem. Ind. 40 
(1921), T.-95. 



Commercial and scientific notes on essential oils. 7 

Oil of Andropogon Iwarancusa. — ^L.Simonsen^) investigated the oil of Andro- 
pogon Iivarcmcma, Jones, a graminea occurring in the Himalayas and the outer hill zone 
from Kashmir to Assam and ascending to 8000 ft. and above, also in the plains from 
North West Himalaya to Bonjbay Presidency. The pale yellow oil, which had been 
obtained in a 1 per cent, yield from the grass, possessed a marked smell of peppermint 
and had the following constants: — d|| 0.9203, [a]Da>o + 51.680, nowo 1.481, acid v. 0.7, 
sap. V. 12.0, sap. v. after acet. 47.4, percentage of ketone, by absorption with neutral 
sodium sulphite solution, 77 per cent. On distilling and refractionating the oil under 
diminished presjsure (200 mm.), the following fractions were obtained: — 1)115 to 130^ 
(14.6 per cent.), 2) 130 to 174 (1.6 per cent.), 3) 174 to 185^ (70 per cent.), 4) 185 to 205^ 
(12 per cent). The first fraction consisted essentially of a hydrocarbon, b. p. 101^ (100 mm.), 
163 to 164° (698 mm.), d|| 0.8565, [ajoaoo -f- 54.82 o, noaoo 1.474, smelling pleasantly remi- 
niscent of cymene. When dissolved in acetic anhydride and treated with a drop of 
sulphuric acid, a transient purple coloration appeared, which rapidly passed into a deep 
brown. When the hydrocarbon was treated with hydrogen chloride in ethereal solution, 
an oil resulted which was probably a monohydrochloride; with hydrogen bromide in 
acetic acid solution a viscous oil was obtained, which was evidently a dihydrobromide 
CioHi8Br2. The hydrogen iodide derivative was very unstable, and decomposed even 
when kept at 0°. Fraction 2) consisted apparently mainly of a mixture of d'A^-p-m^n- 
thenone-3 and the hydrocarbon. Fraction 3) (d|| 0.9321, [«]d3oo + 36.76°, noaoo 1.481) 
consisted, by 98 per cent., of f?-J*-jo-menthenone and was purified by solution in sodium 
sulphite solution and reprecipitation (and racemisation, comp. Read and Smith, p. 34 of 
this Report) by alkali, when it showed the following constants: — b. p. 180 to 181° (200 mm.), 
230 to 231° (697 mm.), d|| 0.9307, [ajosoo + 7.92°, noaoo 1 .481 . Fraction 4) still contained a 
considerable quantity of the ketone. The identity of the racemic ketone with dl-A^-p- 
menthenone-3 = piperitone (comp. p. 149 of this Report) is proved, according to Simonsen, 
by the formation of the benzylidene derivative (m. p. 61°) and the hydroxylamino-oxime 
<m. p. 170 to 171°), furthermore by oxidation of the ketone, by ferric chloride, to thymol 
and by the reduction to menthol. Besides, the author prepared:— the a-semicarbazone 
(m. p. 225 to 227°), the /^-semicarbazone (m. p. 174 to 176°), an optically active /?-semi- 
carbazone (m.p. 193 to 194°), the oxime (m. p. 117 to 118°), and proved thus the identity 
of his ketone with the J>-menthenone-3 obtained by Wallach and others*). The discrep- 
ancies observed in the constants as compared with the values found by former authors 
(a-semicarbazone, m. p. 224 to 226°, /^-semicarbazone, m. p. 171 to 172°, oxime, m. p. 
107 to 109°) are explained by Simonsen by assuming that the compounds obtained 
formerly had not been quite pure and free from isomerides. 

On oxidising the ketone with potassium permanganate solution, at 0°, Z.y-acetyl- 
«-wopropylbutyric acid was obtained; b. p. 195 to 200° (48 mm.). 

Thus the oil of Andropogon Twarancusa consists up to 80 per cent, of drJ ^-menthep- 
one-3 and of. a hydrocarbon of unknown constitution. 

Angelica Oil. — Last autumn, it is true, the Thuringian plantations supplied 
abundant quantites of raw material, but the prices remained high, as there was a 
vivid demand, owing to the completely exhausted stocks of oil. Although we had 
secured considerable lots, our production was scarcely large enough to come up to 
the requirements from all quarters, so that we were almost sold out at the beginning 
of the present year. The prospects are not very favourable, as there are only few 



1) Joum. chem. Soc. 119 (1921), 1644. — «) Comp. RepoHs October 1910, 99; 1916, 18. 



p^r>in- 1923. The shortage of oil will therefore continue. 




Report op Schimmel S Co. 1922. 
tr^sh plantations in Thuringia which, besides, will yield material for distillation only 



w::- 



From fresh angelica roots, Roure-Bertrand Fils*) obtained by water-and-steam 
,.y,> . aistillation 0.4 per cent, of a golden-yellow oil with the following qualities : — di7.6o 0.8887, 
'■, difto 0.8907 (corr.), «i8o+6^42', acid V. 7.20, ester v. 45.07, sap. v. 52.27; soluble in 
2 ^and more vols, of 90 per cent, alcohol. The odour of the oil was inferior to that 
"obtained from dried roots. The low optical rotation and the high acid and ester values 
differed from the normal figures. — The oil extracted from aqueous distillate by means 
of light petroleum showed an odour less intense than that of the principal oil, it was 
dark red and had the constants: — acid v. 20.53, sap. v. 134.40; soluble in 90 per cent, 
alcohol with slight opalescence, entirely soluble in 95 per cent, alcohol. 

Apple Oil. — Basing on their investigations on the composition of ^ the odorous 
principle of ripe apples 'O F. B. Power and V. K. Chesnut^ publish particulars of a 
U. S. Pat. (No. 1366541) for synthetic apple oil. This oil is composed of the woamyl 
esters of formic, acetic, caproic and caprylic acids, together with acetaldehyde, or of 
these components without the isoamyl caproate. According to the abstract available, 
the mixture, which may be employed either in the concentrated state or in alcoholic 
solution, consists of: — woamyl formiate 10 pts., isoamyl acetate 10 pts., woamyl 
n-caproate 5 pts., woamyl caprylate 1 pt, acetaldehyde 2 pts. 

As to the paper published by Kodama (comp. p. 154 of this Beporf) and bearin 
the title: "On the odour of apples; ethereal oils obtained from leucic acid", F. B. Pow 
and V. K. Chesnut*) remark that, according to their investigations, the esters prepared 
by Kodama do not occur in apples*^). Hence, the title given by Kodama to his com- 
munication is not only misleading but entirely unwarranted. 




\>-' 



,'. ' 



Atlas Cedar Tar. — In the well-wooded region of Azrou, south-east of Meknes, 
the natives prepare through incomplete combustion of the roots of Cedrus atlantica, 
Manetti, a tar which was recently investigated by R. Massy®). The author states that 
a long pit, lined with clay and situated on an incline, serves for the purpose. The 
lowest part of it is connected through a narrow pipe with a hole, into which the 
distillation products flow. After having filled, the pit with the pieces of wood from 
the roots, the largest at the bottom, and covered with branches of the tree and sand, 
the wood is lit from the side opposite the escape-pipe, left open for the purpose. The 
slower the combustion, the better the yield. After about twelve hours, the distillate 
collected in the hole is taken out and filled into a hanging skin bag, in which the 
tar separates from the water, this then being removed. The distillation is completed 
dfter another 24 hours, when the new distillate is treated in the same way. 241 kilos 
of cedar wood thus yielded 17.78 kilos (7.4 per cent.) of crude tar, corresponding to 
4 per cent of filtered tar. The final product had the following properties: — daoo 0.981 
to 0.985; on being distilled under ordinary pressure between ISOandSOO^, 71 percent, 
of a dextrorotatory body passed over. The products carried over by steam are dextro- 
rotatory. Less than 5 c. c. of N/soda lye suffice to neutralize the acid contained in 



1) Bull. Roure-BeHrand File, October 19?1, 33. — «) Comp. BeHcht (German) 1921, 7 ; also the work of 
Thomae, BepoHs October 1911, 21 ; April 1918, 28. — ") Perfum. Record 12 (1921), 123. — *) Joum. Americ. 
chem. Soc. 48 (1921), 1741. — ») Comp. Bericht (G-erman) 1921, 7. — •) Joum. de Phartn. et Chim. VII. 24 
(1921), 264. 



Commercial and scientific notes on essential oils. 9 

too c. c. of tar, which acid is soluble in cold water. Every 100 c.c. of tar contain 10.3 
to 12.8 grams of constituents soluble in 5 percent, soda lye, pfecipitable by means 
of hydrochloric acid and soluble again in ether. 
"'. ' ' 

Bay Oil. — According to Robson*), Curator, Mentserrat, the results from the bay 
tree experiment plot in 1919 were mote favourable than ever. Although fifty-two 
distillations were made of leaves reaped from the plot, it was not possible to deal in 
the still at the Botanic Station with the total quantity reaped, and therefore 1255 Ibs^ 
were sold to a distiller at the close of the year. Several thousand pounds of leaves 
were left unreaped on account of the unability to deal with them. Once the trees , 
are' sufficiently developed actually to cover the ground occupied, less and less culti- 
vation is required. The average yield of oil per 100 lbs. of green leaves in this season 
on the whole of the distillations was 17.3 ozs., compared with an average of 18.6 in 
the previous year. The best average results have been obtained between January and 
July. This, however, may be entirely due to the effect of the usual dry weather at 
this time of the year, and to the leaves having a reduced water content as the result 
of evaporation. On the question of the quality of the oil as indicated by the specific 
gravity and the phenol content, the best results in 1917 were obtained in March, April 
and May; in 1918, in June and July; and in 1919, in the month of October. A trial 
was made with old leaves, many of which had been on the trees for at least two 
years, but the result was disappointing in every respect. 

A bay oil from Mexico may be mentioned here just for the sake of its particular 
origin. It was only slightly inferior in quality to good West Indian oils: — d^o 0.9658, 
ojj — 1°50', nDrto r.50891, soluble in 0.5 vol. of 80 per cent, alcohol. A further addition 
of alcohol caused opales6ence. The eugenol content, determined with the aid of 
3 per cent, soda lye, was 55 per cent. 

Birch Tar Oil; — Our repeated endeavours to procure at least small quantities 
of this product, which originates exclusively from Russia, having failed, it was im- 
possible so far to satisfy the demand for this oil, so indispensible for the manufacture 
of a good Russian leather perfume. It is quite understandable, however, that the 
disastrous economic conditions of that country imply that all attention be directed 
for the time being to more important products, so that the users of the article must 
wait patiently stilf longer. 

J. Pritzker and R. Jungkunz') publish an article on the investigation of the oils of 
birch tar and other wood tars. From the review of previous publications^ given by 
the authors, it results^ that the indications regarding the definition of birch tar and 
the parts of the tree used for its manufacture differ considerably. Some say, it is 
obtained from the bark; others^ from bark and twigs, or from the roots, from the 
wood, etc. The authors failed in their attempts to obtain absolutely pure birch tar. 
The results of their investigations show great differences, especially with regard to 
the indices of refraction, which vary between 50.9 and above 100. However, they 
afford some general information, which may be useful for further tests of birch tar oils. 

A product styled „Russian leather fat" (birch tar oil), repeatedly offered in Switzer- 
land, resulted to be a strongly rancid fat, perfumed with some artificial aromatic. 
Two other birch tar oils were strongly adulterated (more than 50 per cent.) with mineral 



») Chemist and Druggist % (1921), 350. — «) Schweiz. Wochenschrift f. Chem. u. Pharm. 59 (1921), 146, 162. 



IjV 10 Report of SchimmelSCo. 1922. 












oils. A pre-war sample of birch tar oil, taken from our research laboratories' collection, 
showed an extraordinarily high content of unsaponifiable constituents, which was not 
due to any admixture of mineral oils. A test for resinous matter gave a negative 
result. Another birch tar oil, surely originating from the neighbourhood of Minsk, 
had the characteristic Russian leather smell and contained 55 per cent, of resin, as 

Jv well as 32 per cent, of unsaponifiable matter of pitchlike character. 

&Y • The author states that Zeiss' butter refractometer answered very well for the 

determination of refraction, whereas Storch's reaction (anhydrous acetic acid and 
sulphuric acid) was a useful test for resinous bodies. As tars from conifers consist 

%{l\ almost exclusively of resin, but tars from deciduous trees contain very little resin, 
the indices of refraction of the various tars and of their distillation products afford a 
!^. means of distinguishing them, especially if the saponification value, the acid value 

and the amount of unsaponifiable products are likewise taken into consideration. 






Oil of Boldo Leaves. — Roure-Bertrand Fils^) obtained from the leaves of the 
boldo tr^e, Pfiumtis BdditSt Mol., Monimiacece, by distillation with steam, a golden-yellow 
oiP), the odour of which resembled that of cineole and chenopodium oil. It showed 
ihe following constants:— di7o 0.9318, diso 0.9334, ano— 0^14', acid v. 1.87, ester v. 13.0, 
cineol content 30 per cent. Besides, the sample investigated contained 10 per cent, of 
constituents soluble in 3 per cent, soda lye. After having been freed from the alkali 
and dissolved in alcohol, they gave a greenish yellow, colour reaction with ferric 
chloride. The acetylated oil showed «di50 + 1°, ester v. 70.93. 

On shaking the distillation water of 40 kilograms of leaves with light petroleum, 
20 grants of an oil were obtained which was much darker and smelled quite different 
from the product obtained direct. It had the following properties: — diso 0.9323, a + 0°, 
acid V. 3.73, ester v. 22.40, ester v. after acetylation 142.18. The authors think that 
the high acetylation value' is due to decomposition products of the ascaridole. The 
acetylated oil smelled distinctly of terpinyl acetate. With the aid. of 5 per cent, soda 
solution, 15 per cent, phenols were separated from the oil, they smelled of carvacrol 
and coloured green with ferric chloride. 

Oil of Boronia pinnata. — The oil obtained by steam distillation from Boronia 
pinnata, Sm., aRutacea occurring in Australia, showed according to Smith') the following 
properties: — amber-yellow colour, aromatic odour like geranyl acetate and geraniol, 
di6o 1.0197, a + 3.8°, noMO 1.5125, saponification v. 20.2, id. after acetylation 36,9, content 
of geranyl acetate 6.4 per cent. The oil contained also free geraniol, geranyl butyrate, 
Irimethyl gallic acid and 70 per cent, elemicin CwHieOs*). 



] 



Oil of Buchu Leaves. — As per the annual statement of trade and shipping of the 
Union of South Africa**), the exports of buchu leaves were as follows: — 

1919 .... 149166 lbs. to the value of 37130^ 

1920 .... 139149 „ „ „ „ „ 67243 „. 

The average annual export for the five years 1910 to 1914 was 204271 lbs., valued 
at 30394 ^, while the average for the five years 1915 to 1919 was 130161 lbs., valued 



1) BuU. Baure-Bertrand Fits, April 1921, 14. — ') Nothing is said about the yield. — ') Proceed. Royal 
Soc. Victoria N. S. 1 (1919), 32. According to Bull. Eoure-Bertrand Fil8, April 1921, 113. — *) There arc no 
other details. — ») Chemist and Druggist 94 (1921), 745. .\ 






Commercial and scientific notes on essential oils.. 11 

at 23937 £, The world's demand for bo^h the buchu ieaVes and oil is rapidly increasing, 
and the future prpspects of buchu as afield crop are good, so that increased interest 
is being taken in the cultivation of the plant. 

s 

Cade Oil. — There are two methods^) of preparing cade oil; viz., the '^destUlatio 
per descensum" for small ■ amounts and the "combustion en milieu confine" for large 
quantities. As A. Juillet^) says, Planchon described in 1911 a new apparatus, which 
is more easily worked and is said to give better yields than the old furnaces. Planchon 
avails himself of the "destUlatio per descensum'\ which he has improved somewhat and" 
carries out on a larger scale. A jug-like container of a capacity of 1 cbm., being 
1 .70 m. high and having a diameter of 0.5 m. in the centre, is used for the dry distil- 
lation of the wood. This furnace, the walls of which are made of bricks and are about 
15 cm. thick, stands on an inclined stone plate, has a small opening on top (diameter 
20 to 25 cm.?) and. another at the bottom, which, is superficially closed djuring the 
distillation with a flat stone. A strong .hemispherical brick-work, which has several 
apertures at the bottom, surrounds the furnace in such a way that the distance between 
the two walls (45 cm. at the bottom, decreases gradually higher up, but the opening 
on top is left free. Through the latter the furnace is filled with pieces of wood of 
Junipervs Oxycedrus, 6 to 25 cm. long. Then the opening is shut by means of a flat 
stone and earth and a fire is made in the space between the two walls and kept up 
for twelve hours. After this time, the walls are so hot that the distillation continues 
for another 6 to 8 hours. The distillation products, flowing out of the lower opening, 
are collected in a large vessel and treated in the well-known way*). 

With this furnace, used in the departments of Gard and Herault (Sommieres), about 
4 to 6 kilos of cade oil can be obtained in one distillation from 250 kilos of wood. 
This yield seems susceptible of an increase. 

The author remarks that there would now be again more demand for genuine cade 
oil, as there was a method of distinguishing between the pure product and faked stuff^). 
The cheap adulterated products form Norway and Asia Minor have no therapeutic value 
at all, whereas the genuine ^article is an excellent remedy against skin diseases, 
especially for animals. 

Mr. B. Menache^), of Barcelona, estimates that 80 tons of pure cade oil are produced 
yearly in Spain, 30 tons of which are consumed locally, and the balance of about 
50 tons are available for export. The cade tree, Juniperus Oxycedrus, L., grows in 
abundance only in the hilly and rocky districts, this is to say far away from railways 
and even carriage-roads. To give an idea of the distance between "civilization'* and 
the cade growing country, Mr. Menache mentions that it takes a two hours' carriage 
journey, followed by a six hours' ride on horsebatk, to go from the railway station 
to his nearest stills, fitted up in 1920 according to the French system®), but with 
iron stills. 

Although the best oil is obtained from the roots alone, generally roots and stems 
s distilled together. Such genuine oils, obtained by Mr. Menach6 in various places, 
id the following properties: — di5o 0.955 to 0.990, completely soluble in ether, soluble 
ith slight opalescence in 20 vols, of 90 per cent, alcohol, colour like burnt sugar. 



*) Comp. i&iwr* November 1908, 24. — ^)Parfum,modemel^{\920),\f^. — *) Comp. Beport Hovember 
8, 25. — *) It is to be regretted that the author does not give any details. We would refer to Huerre's 
vestigations, which might perhaps be useful for the test of cade oil (Report 1919, 9). — ") Perfum. Record 
(1921), 149. — •) Berh Berichte 47 (1914), 2258. 










Report op Schimmel S Co. 1922. 

Years ago, H. Huerre^) showed that direct distillation of the wood of Juniperus 
Oxycedrvs yielded 8.11 per cent, of cade oil, or, if the essential oil had previously been 
removed, only 5.62 per cent, of distillate. In a new treatise, Huerre*) examines the 
relations 'between the content of essential oil in the wood and the yield of cade oil. 
Tfie raw material for his experiments was coarsely powdered wood of Juniperus Oxy- 
cedrus^ from which the essential oil had been drawn by steam distillation and the resin 
extracted by means of ether and acetic ether. This material was subjected to dry 
distillation, partly with an admixture of 3 to 5 per cent, of the essential oil of Juniperus 
Oxyeedrus, partly without. During the distillation, which took four hours, the temperature 
rose after less than two hours from 98 to 203°, then sank to 180° and remained 
constant till the end. In the interior of the wood, it reached 402^ and remained 
constant, after two hours, between 380 and 385°. Six different experiments; carried 
out in this way, had the following results: — 1) In the presence of 5 per cent, essential 
oil: 9 per cent, oil, lighter than water, 32 per cent, water, 9 per cent, tar, 37.5 per cent, 
charcoal. 2) Without any addition: per ceqt. light oil, 36 per cent, water, 2.5 per cent, 
tar, 37.5 per cent, charcoal. 

Huerre concludes from these results that the essential oil of Juniperus Oxyeedrus 
passes over completely with the cade oil and serves as a solvent for the heavy tar. The 
author*s other observation that during the distillation cadinene is transformed only to the 
extent of 20 to 25 per cent, is not new, for F. W. Semmler and W. Jakubowicz^) have shown 
already that a large proportion of cadinene remains unaltered at a temperature of 330P. 

It had been taken for granted that the brown colouring with copper acetate and 
light petroleum sufficed to characterize genuine cade oil. According to H. Huerre*), 
"cade oil for veterinary use*', the origin of which is unknown, gives the identical 
reaction, the same as the essential oils obtained by dry distillation from other conifers, 
with the exception of Finus maritimaipoxT, or Mill.?). The oils of Juniperus Virginiana, L, 
and Cedrus Libaniy Barrel., the same as cade oil, yield after treatment with dilute soda 
lye on distillation under normal pressure 55.5 and 62.5 per cent., respectively, of 
fractions passing over between 250 and 300 o, in addition to a distillation residue of 
7.5 and 10 per cent., respectively. The author intends to publish shortly an article on 
a new reaction of cade oil (by means of the dihydrochloride of cadinene). 

A treatise by R. Massy ^) deals with the tars obtained from African conifers as 
substitutes for cade oil. The author describes the botanical origin of these products 
{Thuja, Juniperus and Cedrus species), the methods of production and the principal 
properties of the tars. 



.i 



Cajuput Oil. — The export figures for the provinces of Ambon and Celebes, including 
those of the island of Boeroe, are now available up to 1918. The direct exports, chiefly 
via Singapore, were: — 



1916 

to British India and China 84000 kilos 
besides, to Java .... 71 000 „ 



1917 

77000 kilos 
83000 



)> 



1918 

33000 kilos 
79000 



» 



Java re-exports a considerable part of its imports. The Javanese use the oil ndt only as 
an embrocation for contusions, excoriations, wounds and head-aches, but also against bugs. 



1) Bull. Sciences Pharmacol. 28 (19i21), 299. As per Chem. Zentralhl. 1»21, IV. 812. — ») Bull, des Trov. de 
la Soc. de Pharm. de Bordeaux, June 1921. According to a reprint kindly sent us. — •) Berl. Ber. 47 (1914), 
2077. RepoH April 191B, 85. — *) Comp. above. — ») Comp. RepoH 1919, 8. 



It 



Commercial and scientific notes on essential oils. .13 

The chief shipping place is Macassar, the official statistics of which port show the 
considerable fluctuations of the last years. 

The shipments were:— 

1914 381 cases or baskets 1918 624 cases or baskets 

1915 4481 ,„ „ „ 1919 2802 „ „ „ 

1916 3359 „ „ „ 1920 1324 „ „ 

1917 .1546 . „ „ „ , 1921 1805 „ „ 

The investigation of a cajuput oil, sent us for the purpose,- showed once again 
very clearly that the constants alone are not always a safe criterion' for the quality 
of the oil. Specific gravity, rotatory power and solubility were altogether normal 
<di6o 0.9209, «D — 0^36', soluble in 1 vol. and more of 80 per cent, alcohol) but the 
odour proved that the product consisted chiefly of a camphor oil fraction containing 
cineole, which ^ad been adjusted to the constants of cajuput oil. The caniphor-like 
odour was so unmistakable that a special chemical proof was not required. 

A great lack of moral sense is required to place such stuff on the market and this 
case shows again how necessary it is to buy only from reliable firms. 

Camphor Oil. — The exports of camphor oil from Japan, after a considerable rise 
in 1920, decreased very much in 1921. In the years from 1919 to 1921, they were as 
follows^):- ^g^g ^Q3Q^ p.^yjg ^^ the value of 333785 yen 

1-920 .... 23424 „ „ „ „ „ 841508 „ ^ 
1921 . . . . 8056 „ » n „ ., 167256 „ \ 

An extensive article in the BnUetin of the Imperial Institute^) on the "Present 
position of the campl^or industry'* deals with the history and, the prospects of camphor 
production in China, japan and Formosa. In addition the cultivation of the camphor 
tree in It^ly, Algeria, South Africa, West Usambara, America, the West Indies, Buenos 
Aires, Burma, the Milgiris, the Straits Settlements, the Federated Malay States, Queens- 
land, Ceylon, Madagascar, Mauritius and the Canaries is discussed with more or less 
details. As our readers will already be fairly well acquainted with the subject, we only 
extract from the article what can serve as a completion of our previous communications. 

Formerly, camphor came to Europe almost entirely in the crude state, from China, 
Formosa, or Japan, the process of refining being a Dutch secret at the close, of the 
seventeenth century and afterwards a Venetian monopoly, but more recently carried 
out in England, Hamburg, Paris, Mew York and Philadelphia, as well as in Japan. — 
1912 it was estimated that 70 per cent, of the world's consumption of camphor*) — 
then 11000000 lbs. — was used for the manufacture of celluloid. Since then, the rapid 
increase of the cinematograph industry has led to a greatly enlarged demand for it as 
a material for the manufacture of films and similar products, such as xylonite. The 
total amount of camphor taken by Europe and the United States in 1914 is said to 
have been 12000000 lbs. 

The Chinese export of camphor in 1891 (before the cession of Formosa) was 
17000 piculs (over 2250000 lbs.), and, according to a Chinese authority, the province 
of Fukien alone had in. 1905 more camphor trees than Formosa. Between 1903 and 
1907, the province was overrun by Japanese employes and, according to the Chinese 



i) Chemist and Druggist 96 (1922), 468. — «) Bull. Imp. List. 18 (1920), 524. — «) It is supposed that 
in the ten first years of this century 7 to 10 million lbs. were'consumed annually, on an average, in the whole 
world, as compared with 17 million lbs. in 1916, 12 million lbs. in 1917 and 10 million lbs. in 1913. 



14 Report of Schimmel S Co. 1922. 

authority already quoted, the |apanese saw that it was only by rapidly destroying the i 

industry in Fukien that they could create a monopoly for themselves. The export of ' 
camphor from Fopchow rose from 264 cwts. in 1902 to 13535 cwts. (1516600 lbs.) in 

1906. As all the available trees were cut down and no planting took place, the industry n 1 

rapidly declined afterwards, as shown by the following table. j 

Total Chinese Exports of Camphor in Pounds:— | 

1907 . . 3433937 lbs. 1912 . . 331000 lbs. 1915 .. . 181735 lbs. | 

1908 . . 1742933 „ 1913 . . 248700 „ 1916 . . 316933 „ 
1911 . . 448133 „ 1914 . . 241333 „ 1917 . . 472933 „. 

The revival under the stimulus of rising prices which is here shown after 1915 
came mainly from the province of Kiangsi, in which there are stated to be camphpr 
forests and some undeveloped territory, especially in the south. In 1919 Kiukiang alone | 

produced 332266 lbs., and the following statistics*) show how considerably the Chinese j 

camphor exJ)ort has revived again since 1919. 

Exports of Camphor from China: - 

1916 .... 2377 piculs ( 316850- lbs.) 181673 taels 

1917 .... 3547 „ ( 472800 „ ) 261918 „ 

1918 .... 5742 „ ( 765400 „ ) 428074 „ ' \ 

1919 .... 23093 „ (3078300 „ ) 1595313 „ 

1920 .... 29997 „ . (3998600 „ ) 2840043 „ . , 

American buyers are looking to China for an immediate addition to the supply, .^ 

as in the Shan States of South-West Yunnan there are stated to be an immense number 
of camphor trees only awaiting transport facilities for their exploitation. The Chinese 
authority already quoted recommends that an American Syndicate should start operations ] 

in South Hunan and South Kiangsi, establishing distillerie^s on modern lines, cutting in 
a conservative manner, and encouraging planting by demonstration plantations, lectures, 
pamphlets, and the free distribution of seed and seedlings, and should afterwards extend 
their action into Kweichow, Kwangtung and Kwangsi. 

In Japan, the export, which had been over 6577000 lbs. in 1889 and about 5860000 lbs. 
in 1891, had fallen to 2961000 lbs. in 1895 2). The exports returned after that date, i.e. j 

after the occupation of Formosa by the Japanese, doubtless include some camphor 
grown in Formosa, so that they cannot be regarded as reliable figures" for Japan proper. 
For this reason, we would only mention the following particulars: — In 1907—8, 
1618 families were engaged in camphor production in Japan, and the production of 
crude camphor was 987922 lbs. In 1910—11, 2615 families produced 1394896 lbs., in .; 

1915—16, 4239 families produced 2117878 lbs.; in the following year, 4329 families only 
produced 2074113 lbs., and in 1917—18 only 3274 families were engaged in the industry, 
and the production fell to less than 1300000 lbs. — For 1919— 20a yield of 4000000 kin 
(5291 000 lbs.) was anticipated, and a return to the normal yield of 5000000 to 6000000 kin 
(6615000 to 7938000 lbs.) for the next year. It is not to be expected that any con- 
siderable share thereof will enter foreign commerce. In 1918, the Japanese industry 
consumed 9600000 lbs. of crude camphor, and in May 1920 all export of crude camphor 
was prohibited, a limited amount of refined camphor being allowed to foreign refiners at a 
discount of 3 per cent, below the market price. In former years nearly all the camphor 
was exported, whereas in China the export was only one-fourth of the quantity produced. 



1) Drug and Chemical Markets 9 (1921), 1206. — *) Comp. also statistics in Gildemeister and Hoffmann, 
The Volatile Oils, 2"<' edition, vol. II, page 473. 



Commercial and scientific notes on essential oils. 1.5 

As stated already iii previous Beports, the Japanese Monopoly Board had started 
since 1900 planting camphor trees on a large scale, hoping for a great success^). But 
in 1918 it is admitted that the e^^pectations to be able to obtain camphor from the 
leaves had not been fulfilled and that the camphor obtained from young trunks was 
not satisfactory. The yield tb be obtained from the planted camphor trees, even in 
another 10 to 15 years, will most likely not be so considerable either, as generally 
pretended. The trees will by then be about 35 years old, whereas the highest yield is 
not arrived at till they are 60 years old. 

Formosa exported 6927000 lbs. of camphor in 1895, compared with 7860000 lbs. 
in 1913, and the following table shows the exports for the years 1915—1919. 

.Production and Export of Formosan Camphor 

to the United States to Europe to Japan 

1915/16 . . . 10389521 lbs. 4211766 lbs. 1798277 lbs. 4379478 lbs. 

1916/17 . . . 11506447 „ 6525489 „ 1726997 „ 3253961 „ 

1917/18 . . . 7945890 „ 4129027 „ 1045345 „ 2771518 „ 

1918/19 . . . 6137732 „ 2055188 „ 913021 „ 3169523 „ 

According to Commerce ^£port8\ it is supposed that the camphqr production in 
Formosa amounted to 6 million lbs., from April 1st ^920 to March 31 «* 1921, exceeding , 
that of the previous year by 275000 lbs. The export, which in |uly 1920 amounted to 
480000 lbs., rose till March 1911 to 600000 lbs. monthly. In the expectation that the 
celluloid industry will revive as soon as the present stocks will have been cleared, 
the Monopoly Board means to increase gradually the quantity of camphor produced. 
Already towards the end of the Chinese administration in Formosa, there existed a 
monopoly for camphor, but as it sustained considerable losses, owing to its reckless 
exploitation and inadequate methods of production, an own monopoly system was 
created for the island in 1899. In 1903 a joint Monopoly Act was passed for Japan 
and Formosa. 

The number of camphor trees growing in the public and imperial forests of Formosa 
is estimated at 12 millions, said to correspond to 27^ (??) million cubic feet of wood. The 
other camphor trees in Formosa, from 100 years of age upwards, are supposed to 
represent 30 million cubic feet of wood, out of which 17500 tons of camphor and 
12800 tons of camphor oil might be obtained*). 

The Government spends 50000 yen annually for planting young camphor trees in 
Formosa. More than 30000 acres have been planted, whereas in Japan proper there 
are only 2000 acres with such plantations. The Government approved of a plan to 
plant 5000 fmho (1 tsubo = 2.5 acres) with camphor trees annually for 1 1 years from 
1918, to protect all the wild trees and to reduce the export as much as possible. 

The production of camphor in Formosa is dealt with in two articles by H. J. Shepstone*) 
and A. B. Kirjassoff ("Formosa the heautiful")% The illustrations regarding the whole 
process of camphor production, as given in Kirjassoff's treatise, are specially interesting 
and instructive. As Shepstone reports, there are nine tribes in Formosa, all of which 
are hostile to each other, and the largest and most powerful is the Atayals, who number 
about 30000, occupying an area of 2500 square miles in the northern part of the island^ 
much of which has never been explored. Head-hunting is the most glorious thing in 
their lives, and a lad is not an adult until he secures a human head. The seriousness 



1) Comp. RepoHs 1918, 12; 1919, 11. — «) Deutsche Allgem. Ztg. According to Chem. IndustHe 44 (1921), 
413. — •) The World's W(yrk, Oct. 1921. As per The Chemist and Druggist 95 (1921), 568. — *) The National 
Geographic Magazine 37 (1920), 241. 



1,6 Report of Schimmel S Co. 1922. 

of their attacks on the camphor-gatherers may be gauged from the fact that during 1914, 
when the statistics were last available, 187 of the collectors wercs killed and 190 wounded^ 

In order to reach the large tracts of camphor forests in the interior, it was essential 
to overcome the savages. The method employed was the establishment of a "guard 
line^ all round the mountainous interior, with small military outposts at intervals, and 
this artificial h'ontier has gradually been extended, so that the turbulent natives are 
confined in a- slowly-diminishing area. As this method was too slow, in view of the 
present state of the industry, the Japanese Government recently voted £ 1000000 to 
bring about a more rapid pacification of the savages, and troops have been sent in 
large numbers. The Formosan native must, therefore, quickly change his attitude 
towards the camphor-gatherers or suffer annihilation. The Government is anxious to 
improve the lot and condition of the natives and to provide education for their children. 

Shepstone says that an average camphor-tree, with a basal circumference of 12 feet, 
will yield about 3 tons of camphor. The felled trees are chopped into chips and 
subjected to distillation on the spot. The chips are placed in a retort over boiling 
water, and, as the camphor vaporizes, it passes through pipes into submerged vats, 
which are so arranged that cool water from a mountain stream can run over them to 
accelerate crystallization^). After the camphor has crystallized, the vats are opened, 
and the product is placed on wooden troughs* to allow whatever free oil there may 
be to drain off. This oil will yield 90 per cent, of crude camphor in the process of 
refining. The crude camphor is packed in tins and carried down precipitous mountain 
paths on coolies' backs to the nearest railway line, whence it goes to the Government 
refinery at Taihoku. 

There are 80000 stills scattered over Formosa. They are in the hands of Chinamen, 
whereas the tree-fellers are Japanese. 

As the Philippine Islands apparently offer favourable conditions for the cultivation 
of camphor-trees, the Government has granted a large stretch of land for this purpose 
to an American company. 

In Ceylon, Mock had begun in 1893 to cultivate camphor-trees in the Hakgalla 
Gardens, six miles from Nuwara Elya, at a height of 5600 feet. The tree thrives best 
at a height of 3 to 5000 feet on chalky soil, also containing potash. As it is not 
sensitive with regard to wind, it is often found as a sort of wind-screen lor tea plan- 
tations*). The twigs and branches yielded 2.7 to 3.4 per cent, of camphor oil and 
0.75 to 1 per cent, of camphor. The output amounted to 143 to 190 lbs. of camphor. 
Bamber and Willis stated in 1910 that the cultivation of camphor-trees was successful 
in Ceylon, if they were plated in rows facing the direction of the predominating winds, 
on sandy clay often watered by rain. Within five years they attain a height of 18 to 20 feet. 

It seemis that at least three different kinds of camphor-trees are cultivated in the 
West-Indies. A tree in St. Vincent, supposed never to have bloomed, over 100 years 
old, and which had been determined Jn Kew as Cinnamomum Camphora, var. glaucescenSj 
yielded on distillation of the wood only oil, but no solid camphor. Another, also 
inferior kind in Trinidad and Dominica is conspicuous by its reddish shoots and leaf- 
stalks and its oval leaves which, on being crushed, smell of turpentine oil. However, 
there are also trees on these two islands, as well as in Jamaica, the leaves of which 
yield 1 per cent, of camphor or more. 



^) It is to be seen from this description that it refers to an improved kind of the usual Chinese distilling 
apparatus, originally employed in Formosa. In Japan proper the production of camphor has been further 
improved. (Comp. Gildemeister and Hoffmann, The Volatile Oils, 2"<' edition, vol. II, page 456.) — ^) Comp. 
Beport 1918, 15. 



L 




Commercial and scientific notes on essential oils. 17 

Cinnamomum Camphora is |Cultivated all over Queensland, where another new 
species occurs, Cinimmomum Oliveri, which is said also to contain camphor. 

In New South Wales, the fresh leaves of a tree, 15 years old, yielded 1.02 percent, 
of camphor. 

A remarkable camphor-tree is found on an island in the Lago Maggiore. When 
eight years old, its trunk was 1 foot in diameter and had the extraordinary height of 
90 feet. Camphor-trees also grow in Buenos Aires, the Canaries and Madagascar. 
On the latter island the wood of trees over 50 years old is used as building material. 

The first camphor-tree plantation in Satsuma, Florida, put 10 000 lbs. of camphor 
on the market since the beginning of this year. The product is stated, to be equal in 
every respect to the Japanese refined camphor. Two companies are said to have 
2500 acres each under cultivation. A third company has been granted permission to 
start a large plantation in Texas ^). 

According to the Befoue agricde de VAfrique du Nord'') several hectares in the 
Doumia Woods (Algeria) have been planted with camphor-trees in 1919. The success 
obtained there, as well as in the districts of Algiers, Blida, Boudjia, El Miliah and 
El Hanser, are supposed to induce the Government to substitute more and more the 
camphor tree to tlje cork-oak in the coastal regions of Algeria, especially in the moist 
East, where the cork of the oaks is* always damp and therefore of no value. According 
to Trabut it would be possible to obtain from a camphor-tree plantation, when 25 years 
old, 300 kilos each of camphor and camphor oil per hectare'). 

According to S. T. Dunn*), it is stated that the direct cause of the presence in 
the camphor-tree of essentiaf oil of varying constitution and quantity is to be found 
probably in the formation within the plant of terpentinol (CioHie)^), which is gradually 
changed by the activity of the living cells into camphor (CioHioO). As this oxidation 
progresses, different compounds appear, ' and it is by their admixture in the products 
of distillation that all- the different oils and finally camphor, itself is formed. "If this 
theory is accepted'^ Mr. Dunn observes, "it is not surprising to find that the yield of 
camphor varies from month to month." Cases are cited to prove that in certain countries, 
notably Japan and Formosa, much more camphor is obtained from camphor-wood cut 
in the cool season than from that cut in the summer. Any other circumstance affecting 
the healthiness and cell activity o\ Cinnamomum Camphora will, it is pointed out, on 
the above theory, also affect the yield of camphor. It is suggested, for example, that 
fungal disease of the wood may have a deterent effect on the production of camphor, 
and it is also noticed, in this connection, that the climatic conditions of North Formosa 
seem to favour a plentiful production of solid camphor, whereas in the South, many 
trees yield little solid camphor, but large quantities of Sho oil and Yu-yu oil, the trees 
being known to the Japanese as Sho-gyu and Yu-yu, respectively^. In the climate of 
Florida the same species produces solid camphor mixed with an oil differing from the 
Japanese oils in its low percentage of safrole. Remarkable variations of camphor content 
in the leaves of trees growing under different conditions*of shade and soil have also 
been recorded'). Experiments in Kew have shown that, apart from two slight colour 



*) Joum. Soc. Chem, Ind. 40 (1921), R. 388. — ») Parfum. r^odeme U (1921), 212. — •) Comp. Beport 
April 1908, 23; Bericht (German ed.) 1920, 13. — *) Bull, of Miscellaneous Information no. 4, 1921. As per 
Perfum. Becord 13 (1921), 323. — ») The designation of •terpentinol" for hydrocarbons CioHu is, of course, 
absolutely incorrect. — ^) According to Kf Nagai, the Shd-Gyu and the Yu-Ju trees, the botanical origin of 
which is still unknown, are not identical with Cinnamomum Camphora. The Yu-Ju oil has a great resemblance 
with camphor oil. Comp. Gildemeister and Hoffmann, The Volatile Oils, 2"^ edition, vol. Ill, page 672. — 
') Comp. also Beport 1918, 15. 

2 






18 



Report of S'chimmel 8i Co. 1922. 






(&..■>. 









m-: 



>fi' 



k< 



(V. 



■•'»;•'- 



''V- 









p. 



V 



t: 



indications, no visible varietal characters can be found in any part of the tree to 
separate **camphor'* trees from "oil" trees. Dunn suggests the following lines. of 
improvement for plantations of camphor trees: (1)* Seeds should be secured from trees 
known to produce camphor, (2) suitable climate and soil should be selected, (3) saplings 
must be planted so that they may be clipped conveniently; (4) the best months for 
clipping must be ascertained by experiment, as observations show considerable changes 
in the camphor content of the leaves as the growing season advances. 

^ Cananga Oil. -r- It is reported that the distillation of this article in )ava is no longer 
remunerative at the present price obtained for it in Europe, i.e. 10 to 12 Dutch Florins 
per kilo, especially because the producers lack cheap fuel. According to our informants, 
the distillation stopped, almost completely in 1921, all the oil shipped being of 1920 
production. As the wages for the collectors of the flowers have doubled since the 
war, the distillers prefer waiting until they know the consumers* attitude with regard 
to the higher prices that are to be expected. 

Caraway Oil. —The Dutch caraway market was very firm throughout the year 
1921. Owing to the smajll crop (only 15000 bales, i. e. even less tjian in the previous 
year), the prices rose during the summer up to about 17 florins, but towards the end 
of the year they went 'down a little, to 16 florins, as there was rto very keen demand. 
The stocks of old caraway, which had agglomerated considerably, as we reported 
previously, have gradually been disposed of, so that the average quality .was better 
than in 1920. One expects very little, of the 1922 crop, in fact less than the year 
before, as the seedlings from spring 1921 had to be ploughed under, owing to the 
drought in autumn. The quantities available up to the next crop but one, L e. in 
August 1923, will most likely ^Drove insufficient for the world's requirements, so' that 
very high prices are to be expected. 

As regards the caraway market in 1920, some information from the Dutch Board 
of Agriculture is now available*), from which we gather that the area under culti- 
vation was 971 hectares. The crop was small, but there were still considerable stocks 
of old seed. There was but little business with Central Europe; England and the 
United States, however, took again the usual quantities. The prices ranged from 
22 down to 15 florins. Owing to high rent, big wages and expensive manure, the 
cultivation is said to have become unprofitable, so that it is to be feared that it will 
be given up. The exports in 1920 totalled 3767 tons to the value of 1412000 florins. 

There were fairly considerable offers of East-Friesian and East-Prussian caraway, 
but unfortunately the largest part by far was exported, as the prices paid abroad were" 
tempting. Only comparatively small lots were available for distillation in the country. 
It is to be regretted that the German Government have not realized so far, how necessary 
it is to stop the exports of caraway seed. On the other hand, one is pleased to see 
that the German farmers have given far more attention to the cultivation of caraway 
and that the success is visible already. 

Oil of Cathetus fasclculata. — In the course of this year we received two samples 
of the so-called Bruyere oil, distilled in Annam (Further India) from the Euphorhiacea 
Cathetus fasdculafa, Lour. As the oil is but little known, we think the following parti- 
culars will be of interest: — The samples were pale yellow and yellow, respectively. 



^) Versing omtrent Handel, Xijverheid en Scheepvnart van Nederland gedurende 1920. 



Commercial and scientific notes on essential oils. 



19 



and their odour recalled cajuput oil, dieo 0.8826 and 0.8905, ap — 2^9' and —5026', 
noMo 1 .47730 and 1.47926, acid v. 1.1 and 1.8, ester v. 4.3 and 4.2, soluble in 0.5 and 
3.5 vols., respectively, of 90 per cent, alcohol. Of 80 per, cent, alcohol even 10 vols, 
were insufficient for a solution. 

These properties tally on the whole with the indications regarding Bruyere oil in 
Gildemeister and Hoffmann, The Volatile Oils, 2"«^ edition, vol. Ill, page 146. 

Chatnottiile Oil. — According to an English peribdicaP)t oil of chamomile is 
a suitable solvent for platinum chloride. It is said to be used for this purpose in 
the glass and porcelain industries, in order to coat vessels with platinum. 

Chenopodiutti Oil. — See Wormseed Oil, p. 80 of this B^ort 

Cinnamon Oil, Ceylon.— The demand for cinnamon' oil and, in a still higher 
degree, for cinnamon leaf oil has increased considerably during the last years. The 
latter can be obtained in a satisfactory quality^ from Ceylon, the Seychelles and 
Mauritius, whereas it seems to be impossible so far to distil a good bark oil from 
raw material of other origin than Ceylon, although it is reported that cinnamon bark 
from the Gold Coast has yielded in the last years valuable oils of agreeable odour^). 
The area planted with cinnamort trees in Ceylon has decreased continuously, as other 
plants, like caoutchouc-trees and coconut palms pay better. The latest official estimate^) 
of the total area under cinnamon is about 35000 acres, as compared >yith 48000 acres in 
1909. The cinnamon gardens of Ceylon are situated chiefly in the Southern and Western 
Provinces of the island. The following tables give details of the exports from Ceylon:^— 

Annual* average export of cinnamon bark from Ceylon during the decades 





. 1841 to 1850 . 




• 


. 529461 lbs. 


52497 £ 


*) 






1871 „ 1880 . 






. 1274668 


II 


64649. „ 




< 




1881 „ 1888 . 




• 


. 2088232 




107604 „ 




1 




1901 „ 1910 . 






. 5565684 


n 


171395 „ 




. 




1911 „ 1920 . 






. 5155470 


« 


134760 „ 










Exports from Ceylon 






. 


Year 


Cinnamon 


bark 6) 




Cinnamon 


bark oil*) 


Cinnamon leaf oil 


1909 . 


. . 6501040 lbs. 


181913 £ 










— . 


1910 . . 


. . 6306060 „ 


186219 


n 


90710 OZ. 


1618 .£ 


76008 


oz. 


519 jf*) 


1911 . . 


. . 5773140 „ 


139086 


M 


49502 „ 


1131 „ 


63600 


i» 


453 „ 


1912 . . 


. . 5945632 „ 


188992 


»» 


65972 „ 


1417 „ 


34020 


II 


186 „ 


1913 . . 


. . 5140800 „ 


160908 


11 


161t2 „ 


715 „ 


52092 


11 


JM „ 


1914 . . 


. . 4080272 „ 


107777 


>I 


10129 „ 


673 „ 


36936 


11 


228 „ 


1915 . 


. . 6451984 „ 


133178 


» 


OO Ot^o „ 


1698 „ 


64692 


« 


1061 „ 


1916 . . 


. . 5012896 „ 


83713 


» 


62132 „ 


1620 „ 


120874 


» 


1809 „ 


1917 .. . 


. 3328192 „ 


64518 


II 


78438 „ 


2655 „ 


95091 


n 


1199 „ 


1918 . . 


. . 4187680 „ 


89900 


M 


62283 „ 


5109. „ 


258020 


» 


5048 „ 


1919 . . 


. . 7700560 „ 


246393 


» 


66773 „ 


5655 „ 


299928 


M 


6274 „ 


1920 . 


. . 3933552 „ 


143141 


»> 


73246 „ 


2572 „ 


365976 


» 


5553 „ 



.1) T&rfum&r'a Journ. & Essential Oil Recorder. As per Deutsche Parf. Ztg. 7 (1921), 95. — *) Cf. Biricht 
(German) 1920, 66. — ») Bull. Imp. Inst. 19 (1921), 319. — *) Converted from rupees at the rate of Rs. 15 = jf* 1 . 
— *) Cinnamon bark includes quills and chips. — *) The cinnamon bark oil exported from Ceylon was as 
a rule strongly adulterated with cinnamon leaf oil. 

2* 






I ■■:*■> 






■ V 
f 

J* - 

Pi.',.*' 
» * 



l^'i 



P >/ 20 Report of Schimmel a Co. 1922. 

^^v-V. Before the war Germany was, as a rule, the largest buyer of both quills and chips; 

£*>' ^' other important countries to which the bark was shipped being the United Kingdom, 

^':y\ Spain, Holland, Italy, the United States and Belgium. In 1920 Germany again became 

an important buyer 218736 lbs. of quills and 134176 lbs. of chips, against 4928 lbs. of 

quills in the year before, in that year the United States being the chief buyer of quills. 

The best cinnamon is grown in Ceylon in a very sandy clay or fine white quartz 

j„, . sand, with a good rich sub-soil, at altitudes of less than 1500 feet, in the strip of 

^i?;; land 12 to 15 miles wide, on the south-west coast, between Negumbo, Colombo and 

Matura. The tree is usually grown from seed in nursery lines and transplanted when 3, 

4 or 12 months old. Sometimes it is propagated by cuttings of very young three-leaved 

i^x: shoots, or by layers. Adult trees flower in May and fruit in |uly; and, unless bagged 

l^- for seed, the entire crop of fruit is liable to be eaten by birds. The ripe fruit is 

heaped in the shade until the pulp turns black and rots, when the seed can be removed 

by trampling; the seed is washed and dried in the shade before sowing. ~ Cattle, 

goats and squirrels nibble the young shoots; but otherwise cinnamon is not very liable 

fi:. to animal or vegetable pests. Pestalozzia cinnamhmi, Raciborski, is a minute leaf and 

^ twig fungus; and the "pink disease" {Corticium salmoni-color, B. and Br.), a wet season 

> disease, well known as attacking Para rubber, forming a pink crust on the stem and 

• destroying the cambium, a sign that the trees are over-crowded, also occurs and can be 

dealt with by spraying with Bordeaux mixture and excising and burning affected parts. 

In order to obtain the bark, the shoots, usually two years old, averaging 3 to 4 feet 

in length and 0.5 to 0.75 inch in diameter, are cut in May or November, when the sap 

moves and facilitates peeling. The slips of bark are heaped together and covered over 

for a day or two, so as to undergo, perhaps, a slight fermentation*) which facilitates 

the scraping off of' the epidermis and pulpy hypoderm in the process known as 

I "piping". The slips of bark contract into pipfes or "quills", which are packed one 

inside the other,, cut square and of uniform length, dried in the shade and ultimately 

in the sun, and eventually made up into bundles of 100 lbs. weight. The prunings and 

waste pieces obtained in peeling are known as cinnamon chips. They have only been 

exported from Ceylon since 1867 and have been used since 1872 chiefly for distilling 

cinnamon oiP). 

There is no evidence of the cultivation on any commercial scale of the true 
cinnamon (Cinnamomum zeylanicum) in India, though it may be represented as a wild 
tree in the Western Ghats. But various barks and twigs are sold as Cassia lignea 
originating from other Cinnamomum specias, such as C. Tamald, Nees et Eberm., 
C. obtimfolium, Nees (closely allied to C, Cassia^ Blume), C. iners, Wight') (according 
to Thwaites and Ridley only a coarser form of C. zeylanicum, like C. nitidum, Blume, 
and some others)*) and C. macrocarpumj Hook. fil. The essential oils of these drugs 
are used partly for adulterating the genuine cinnamon oil, partly in the soap industry. 
Cinnamon trees were introduced into Seychelles with other species, about 1775, 
from the Dutch East Indies, and were for a time cultivated in the Royal Gardens at 
Mah6. The trees spread through the forests and were neglected until 1908, in which 
year 1202 tons of bark were exported. At the same time distillation of oil from the 
bark of the wild trees was commenced. The bark differed but little in appearance 



^) The fresh white bark turns red on drying, owing to the formation of phlobaphene. A fermentation 
is not very likely to occur. — ') Cf. Gildemeister and Hoffmann, The Volatile Oils, 2^^ edition, vol. II, p. 419. 
— •) According to the Index KeioensiSf Cinnamomum iners, Wight, is identical with C. zeylanicum. — *) Dymock, 
Pharmacographia Indica, 1898, vol. Ill, p. 208. 



Commercial and scientific notes on essential oils. 



21 



from that of the trees cultivated in Ceylon *), but it was never handled so carefully, 
never had the fine aroma of Ceylon cinnamon*) and in consequence never fetched so 
good a price. The exports of bark from Seychelles for the years 1908—1919 are shown 
in the following table: — 

1908 .... 1202 tons 1915 .... 189 tons 



1 y\j\j . . . < 

1909 . . . . 


1044 


1910 . . . . 


731 


1911 ... 


. 964 


1912 . . . . 


1098 


1913 . . . . 


698 


1914 . . . < 


. 589 



If 



» 



w 



l» 



n 



n 



1916 . . . 


. 184 


1917 ... 


1 


1918 . . . 


nil 


1919 . . . 


. 275 


1920 .. . 


. 185 



n 



ti 



n 



» 



>» 



Prior to 1915 most of the bark was shipped to Germany, Holland being the next 
most important customer. In 1915 and later years the bulk went to the United Kingdom. 
After twelve stills had been installed in 1915 for the distillation of cinnamon bark and 
leaf and lemongrass oils, the exports increased sevenfold within three years. During 
the war the development of the industry was hampered by the impossibilty of obtaining 
modern machinery for steam distillation from Europe, but a Chinese settler set the 
example of building a small still of wood and iron obtained locally for direct fire 
distillation: his example was followed by many small-holders. On samples bping 
submitted to the Imperial Institute, it was found that there was not, much difference 
between the oils obtained by steam distillation and those from direct fire distillation. 
The high price reached by cinnamon leaf oil encouraged the manufacturers to devote^ 
themselves mainly to this oil, as is shown by the following table of exports, and during 
1920 there were 44 distilleries at work (total production 24430 litres)^), as against 12 in 1915. 

Export of Cinnamon Oils from Seychelles. 



Bark oil 



Leaf oil 



1911 . . . 


1 I 


0,2 £ 


212 1 


56 ^ 


1912 . . . 




• 


1543,, 


338 „ 


1913 . . . 


, 




3054,, 


- 799 „ 


1914 ., . . 






8406,, 


2320 „ 


1915 . . . 


99 


73 „ 


9587 „ 


2505 „ 


1916 . . . 


. 1834 „ 


1041 „ 


15669 „ 


4484 „ 


1917 . . 


. . 91 „ 


171 .. 


14 175 „ 


4317 „ 


1918 . . . 


■ 131 „ 


262 „ 


12731 „ 


5111 „ 


1919 . . 


. . 27 „ 


46 „ 


24430 „ 


11634 „ 


1920 . . 




• 


39507 „ 


26029 „ 



The price of cinnamon leaf oil having fallen from 10 rupees to about Rs. 3 to Rs. 4 
per litre in 1920^), little has been manufactured since, so that the exports for 1921 will 
show a decline. 

Up to 1911 no difference was made in Seychelles between bark and leaf oils. The 
exports of "cinnamon oil" were 285 litres in 1908, 12 litres in 1909 and 124 litres in 1910. 

A number of trees having been planted near Malacca, a small quantity of quills 
were prepared in 1851 by Sinhalese convicts, who were professional cinnamon peelers, 
and sent to England, but although, considering that the bark was cut at the wrong 
season and from neglected trees, the report was favourable and the bark was paid 



1) Cf. BepoHa April 1910, 35; April 1911, 43. — ») Cinnamon oil from Seychelles differs also from the 
Ceylon product in that its content of cinnamaldehyde is lower and that it contains camphor. Report November 
1908, 42. — 3) As per Heil- und Gtiviirzpjl. i (1921), 127. — *) Perfum. Record 12 (1921), 415. 



22 Report OF ScHiMMEL a Co. 1922. 

lairly well, the cultivation was not proceeded with, probably on account of the law 
prices which have since prevailed. ^ Various other species of Cinnamomum occur in 
a wild state in the Malay region, some of which, such as C tavoyanum. are altin to 
■ C. Cassia, whilst others, such as C. Farthenoxylon, are more allied to C. Camphora. 
C. CulUawan, Blume, the clove bark') of the Malays (Kulit ^ bark, Loirang == clove) 
is a native of both the Peninsula and the islands. The calyces of the fruit are used 
locally in medicine and curries under the name ot "bunga Idjeang" (clove flowers). 
The cultivation of Cinnam<mum zeylanimm was introduced into the Dutch East 
Indies (Java) in 1825, as it seemed with success in the beginning. It resulted after- 
wards, however, that the fine quality of the genuine Ceylon cinnamon could not be 
attained, and from 1865 the cultivation gradually died out. The tree is now grown 
only on a small scale on a few European estates. — A trifling quantity of bark is 
derived in |ava from C. Cassia and the rest from 0. Bvrmanni, Blume*), a tree growing 
wild throu^out the Malay archipelago. It is a slender tree occurring chiefly in the 
mountains, and the bark is stated to Improve in quality the greater the altitude at 
which it Is grown. The better qualities of bark are from the trunk, the second quality, 
which is lacking in flavour, being derived from the thicker branches. The United States 
has been the chief purchaser of the product, Holland taking the bulk of the remainder. 
Total Exports ot Cinnamon Barks from the Dutch East Indies (Padang, |ava and 
Macassar) in the years from 1908 to 1912: — 

1908 ... 752 tons = 22916 ^' 

1909 . . . 1016 „ = 32833 „ 

1910 ... 1297 „ = 37333 „ 

1911 . . . 1922 „ = 22250,, 

1912 .- . . 1032 „ -- 23666 „ 

Both Cinnamonmm zet/lanicwm 0. Cassia have been successfully grown in Fiji from 
seed, and the *ark and the leaves distilled on a small experimental scale at WMirau"). 
The cinnamon was planted in 1906, and is stated to have become quite naturalized, 
the seeds being distributed through the forests by pigeons. 

As to the West Indies, cinnamon was found by Captain Marshall in, 1782 in 
St. Domingo. It was sent to Jamaica and has since been grown in the island, but not 
*on any considerable scale. A bark frequently known in the drug trade as "wild or 
white cinnamon", is that of Canella alba, Murr,, a Wirteranacea. In no way related to the 
true cinnamon. It is a native of IHorida and the West Indies, and has been known as 
"lamalca Winter's Bark" and "lamaica Cassia lignea" but is now shipped mainly from New 
Providence in ttie Bahamas under the names of "White Wood Bark" or "Cinnamon Bark". 

S6me data from an English source^) as to the history of cinnamon barks") whichj 
as it is well known, belong to the oldest spices, will certainly interest our readers. 
According to D. Hanbury none of the cinnamon of antiquity was derived either from 
Cinnanwmvm neylanicum or from Ceylon. The very name "cinnamon" from the.. Arabic 
''mama" or Greek "amomum" (meaning spice) and the prefix "chivi". Chinese, which 
persists in the Persian and ffindustani "Darchini", suggests the Chinese origin of the 
drug, and under the name "if W, which forms part. of several Chinese place-names. 



or cent, ol eugenal and lame methyl-cueenol. Ci. Gild 
<[.ll, p.439. — •)Aaloi)il>(tomthebBrkot<»H>iain(nnu 
nn>, Blume, see Cildeineister and Horfmann, Tlit, V<,talih OOi, ^' edition, vol, 
■ic, Fiji. 1B11, p. 7; 1818, p. 6. A» per Bull. Imp. /«>!. » (mi). 338. There are i 
publication. — ') BuH. Imii. Jmrf. lit (1921), 321. — ') CI. also Qildemeiater fli 
J., 2"" ed,, vol. I, p. 135. 



Commercial and scientific notes on essential oils. 23 

cassia is mentioned in the earliest Chinese herbal, sajd to have been written in 2700 B.C. 
The mention of ""Tien-chu ktcei", that is Indian cassia, in the Pen-tsao, written in the 
eighth century may refer to bark produced in Malabar. The mention of two spiced or 
perfumes, cinnamon and cassia, in the older, books of the Old Testament and in the 
earliest Greek works on medicine, as nearly allied but of different value, may have 
only referred to two qualities of what we should now call cassia, this latter name 
— originally ''casta" — being related' to the Hebrew "ketzioth'% meaning "stripped off**. 
The barks were originally brought to^urdpe — that is ic the Levant — by Phoenicians, 
who obtained them from the Arabs, and the ancient notion that they were derived 
from a "regio cinnamomifera" in Somaliland may have been merely an error arising 
from this trade passing through several hands or part of the common characteristic 
system of trade mystification. The full Arabic name "Kirfat-ct'darsini", bark of the 
Chinese tree, shortened into "Kirfah", persists as "Kalfah", the existing Bombay name 
for Malabar cassia. As Sir Emerson Tennent ^pointed out, there is no mention of 
cinnamon as a product of Ceylon prior to the Arab writer Kazwini, about A. D. 1275, 
and the Minorite friar, John of Montecorvino, about 1293; and Hanbury makes the 
highly probable suggestion that the Chinese, who were acquainted with 0. Cassia, a 
very similar tree, and who traded with Ceylon and the coast of Malabar, were con- 
cerned in the discovery of the value of the Ceylon bark. The Chalias, the caste to 
which the peeling and preparation of cinnamon bark is now restricted in Ceylon, are 
said to have emigrated from India in the thirteenth century; and in the following 
century Mohammedan writers' were well acquainted with Ceylon cinnamon and the 
difference between it and Chinese and Indian cassia. One of them, writing in 1368 of 
"DarchinV\ says "the best is that which comes from Ceylon", while the best Chinese 
cassia C'salikheh") is, he sayS, thick, reddish, a little bitter and astringent, but sweeter 
than Indian Kirfah which "tastes like cloves". • ; ^ 

The Portuguese, arriving ,in Ceylon in 1505*), found the cinnamon in a wild state, 
and exacted a tribute of 250000 lbs. of bark annually from the Sinhalese king. Garcia 
da Orta, about the middle of the same century, speaks of Ceylon cinnamon as worth 
four times as much as that from Malabar, and the Portuguese occupation of Ceylon 
in 1536 is stated to have been accomplished chiefly for the sake of the cinnamon. 
After the Dutch conquest in 1656 the Government monopoly of the export of bark was 
strictly maintained, but it was under the Dutch auspices that, about 1770, the cultiva- 
tion of the tree was commenced. The entire European demand-, stated to have been 
about 400000 lbs. a year, was then supplied from Ceylon; and, after the British con- 
quest in 1796, the annual production, during the monopoly of the East India Company, 
which lasted until 1833, did not exceed 500000 lbs. The Dutch began the cultivation 
of the tree in Java in 1825, and, while a heavy export duty was imposed on Ceylon 
bark until 1853, the competition of Javanese bark and of Chinese cassia told upon the 
Ceylon industry. 

Cinnamon barks and chips from Madagascar, received by Roure-Bertrand Fils*), 
yielded on steam distillation 0.17 percent, of essential oil of the following properties: 
di7o 0.9715, di6o 0.9731, «i7o — 5^49', acid v. 2.49, aldehyde content 48 percent.; in- 
completely soluble in 70 per cent, alcohol, soluble in 1 vol. of 80 per cent, alcohol ; on 
addition of more alcohol, turbidity which disappeared again, however, when the 
quantity of alcohol reached 10 volumes. 



N/ 



^) Vasco da Gama reached the coast of Malabar already in 1498. — *) Bull. liofire-Bertrand Fits, 
October 1921, 35. 



24 Report of Schimhel Ei Co. 1922. 

From the distillation water 0.3 percent, of an entirely different oil could be 
extracted with Ugfit pefroleum: di,o 1.0281, d,»o 1.0297, i„o — 2=2', acid v. 2.49, alde- 
hyde content 82 per cent., soluble in 1.75 vol. of 70 per cent, alcohol and in 0.75 vol. 
of 80 percent alcohol, further addition of alcohol caused slight turbidity. A mixture 
of both oils had the following constants: dno 1.0075, d,6o 1.0091, b„d — 3^23', acid v. 
2.49, aldehyde content 70 per cent., soluble in 2 vols, of 70 per cent, alcohol ; slight 
turbidity on further addition of alcohol. The oils referred to were amber-yellow, their 
odour reminded one somewhat of Ceylon cinnamon oil, but they did come near the 
quality of the latter. 

Cinnamon Leaf Oil. — Little has been pviblished so far on cinnamon leaf oil from 
South Kanara; the more interesting therefore what C. K. Menon') says about it. The 
cinnamon tree, Cinnammnum zei/lankwn, IHees which according to Tschirch occurs in 
the south-west of British India in very different forms'), all belonging to the same 
spcfcies, however, grows abundantly in the coast district of South Ranara at elevations 
varying from 100 to 700 fest — and fairly up to 3500 feet on ttie Ghat slopes. The 
local distillers distinguish four kinds of trees from the taste of the leaves, w., "mitta" ■ 
(sweet), "pUika" (insipid), "tej" (pungent), and "kadira" (bitter). They collect the leaves 
only of the last two for oil extraction, the first two are reported to be useless tor this 
purpose. In Ceylon the leaves are macerated in sea-water and subsequently distilled, 
but in South Kanara the first operation is not carried out. In that district the rude 
apparatus for distilling the leaf oil consists of three earthen pots, serving respectively 
as boiler, covering pot and receiver, with two short bamboo tubes to conduct the steam 
from the boiler to the condenser. The large earthenware pot which acts as the boiler 
is placed over a furnace; water is poured into it to a depth of 9 inches. Fairly 
matured green leaves ar& packed into it A small earthenware pot is kept with 
its mouth down over the boiler, the joint t>eing well plastered with clay and cow-dung 
mixed. A small bamboo tube, about a foot long and half an inch' In diameter, is 
thrust through a hole in the top of the upper pot. To the free end of this tube, 
another about three feet in length is attached, the two joints being wrapped up in 
cloth and plastered well with the, clay mixture. The longer tube Is led into the con- 
denser, fixed in a tank containing cold, muddy water. A thick wet cloth is spread 
over the mouth of the condenser, and around the bamboo tube. The muddy water is 
replaced as It gets heated. Tfie water in the boiler is heated to boiling point; the 
steam and the extracted oil are condensed against the cool sides of the condenser. 
The oil being heavier than water, sinks to the bottom. 

The working season lasts only from November to IVlarch, after which the young 
leaves appear, and these would not yield sufficient oil to repay the labour. In Morth 
IMangalore Forest Division of the South Kanara district cinnamon areas in the un- 
reserved lands are divided into working circles; each one is intended to provide leaves 
for five stille annually during the working season. The number of local distillers is 
fixed, and each working circle is auctioned to a single individual. 

Menon suggests that cinnamon growth should be concentrated within small and 
compact areas, instead of continuing the present system. The plant can easily be 
grown from seed. The average annual production is about 25 tins of oil (I tin = 
24 bottles = 18 litres), which is sent to Bombay, the chief market for South Kanara oil. 



Commercial and scientific notes on essential oils. 



25 



Citronella Oil from Java. — The Java export figures from January up to the end 
of November 1921 have now been published as follows: — 



Holland. . . 
Qreat Britain. 
Germany . . 
France . . . 
United States 
Singapore . . 
China . . . 
Japan . . . 



n 



II 



II' 



« 



It 



n 



>f 



n 



n 



30373 kilos 

8356 
10040 
26331 
92118 

8391 

8235 
64029 
Other countries . 889 „ 

248762 kilos. 

The exports in the last three years totalled: — 

1918 » 228000 kilos 

1919 = 528500 

1920 « 434500 
the separate figures being: — 

Destination 1918 

Holland — 

Great Britain — 

France — 

Switzerland ...... — 

United States 84000 

Singapore 46000 

Hong Kong ...... 5000 

China 4000 

japan 81000 

Australia 1500 

Germany — — — 

Other countries' .... 6000 1000 — 

The low figures for Germany are explained by the fact that she had no direct 
steamer connection with the Dutch Indies during the period referred to. Her real 
consumption is contained in the figures given for Holland. 

Australia bought as long as there was little or no Ceylon oil available. Singapore 
and Hong Kong are only places of transit. 

As it will be remembered, the total export of Java citronella oil was 426000 kilos 
in 1916 and 515000 kilos in 1917. The diminution by nearly 300000 kilos in 1918 was 
due to shipping difficulties, which were overcome only gradually in the course of 1919. 
Since then the costs of production have risen considerably, owing to the upward 
movement of the wages in 1919 and 1920. Besides, various factories of medium size 
have become State property by repurchase or expropriation on account of older 
claims and they have been closed, as such factories do not lend themselves to bp 
managed by the State. A somewhat correct estimate of the total production can only 
be based on the average export figures of several years, the available data regarding 
the area under cultivation being inaccurate. In competent quarters the average annual 
production is estimated at 350000 kilos, for the distillation of which 60000 tons of 
citronella grass would be required, supposing a yield of 0.6 per cent. The total 
production in 1921 is stated to have been about 320000 kilos. 

Of the above-mentioned shipments of 248762 kilos for the time from January to 
November 1921, only 82000 kilos were forwarded during the first six months, as the 
prices then left very little profit. Business revived as soon as the market improved. 



1919 


1920 


233000 


124000 


91000 


75000 


69000 


.80000 


6000 




85000 


76000 


24000 


44000 


6000 


1000 


2000 


9000 


7000 


19000 


3000 


4500 







Report of Schimmel Sj Co. 1922. 



_ 'k ' 






?.*" 



jvy 



i/':< 



Tht production is said to have gone down considerably during the isummer months, 
owing the extraordinarily dry weather. ^ 

A citronella oil from the. Seychelles of the year 1918, investigated by the Imperial 



Institute*) had the following constants: — dj^ 0.881, «djoo — 28^30', soluble in 1.7 vols. 
IW per cent, alcohol at 20^, turbidity with 10 vols., insoluble in 80 per cent, alcohol 
at 15^. Total geraniol (all acetylizable constituents calculated as geraniol) 52.2 per cent, 
gefaniol 27.5 per cent., citronella! 24.7 per cent.*). Compared with other citronella oils, 
the sample resembled somewhat the Ceylon product. The citronella grass, from which the 
sample in question had been distilled, had been imported from Ceylon to the Seychelles. 

Clove Oil. — For the time being there are no special reports on the Zanzibar 
clove market. — Only 10 to 15 tons of the Madagascar cloves come from the main-, 
land, the larger part being gathered on the island St. Marie, situated near the north- 
east coast The exports, chiefly to France, were 143 tons in 1918 and 499 tons in 
1919. Although the shipments in December 1920 amounted to 87 tons, the whole 
1920/21 crop totalled only 20 tons. The prospects for 1921/22 are said to be good*)- 

Oil of Coleus amboinicus.^— According to F. Weehuizen*), the leaves of Golem 
amboi/nicus, Lour.*) (C. carnosus, Hassk.), a labiata indigenous in Java, contain an essential 
oil (0.055 and 0.021 per cent), in which the presence of carvacrol could be proved. 

Copaiba Balsam Oil. — In order to avoid the often disturbing influence of con- 
centrated sulphuric acid, |. B. Luther^) carried out Turner^s reaction for the determination 
of gurjun balsam oil in copaiba balsam oil as follows: — After having added 1 drop 
of a 10 per cent solution of sodium nitrite to a solution of 4 drops of the oil in 1 cc. 
of glacial acetic acid, this was mixed at once with 2 cc. of glacial acetic acid containing 
5 per cent by volume of concentrated sulphuric acid. The presenee of gurjun balsam is 
revealed at once by a violet colour. Copaiba balsam turns red within a short time^. 

Coriander Oil. — Thuringian coriander was on the market in fairly considerable 
quantities, but the prices asked for were so high that our industry bought with the greatest 
reserve. The depreciation of the Mark caused in this case too that nearly the whole 
production was exported at high prices to the detriment of the home Industry, for in the 
end the manufacturers of essential oils had to buy at export prices in order to replenish 
their stocks. It seems, unfortunately, that the Government little grasps the situation for, 
as with caraway and fennel, no reply has been given to a motion to stop the export. 

In order to ascertain something about the effect of bleaching on coriander, 
). A. Baker ^ treated the drug with sulphur dioxide. It was found through quantitative 
experiments that the action of a 1 per cent solution of sulphur dioxide during one 
minute was quite . sufficient to bleach coriander. This process answered better than 
a twenty-four hours* dry treatment of the seeds with double the quantity of sulphur 
dioxide. Whereas unbleached coriander yielded on steam distillation 0.185 per cent 
of essentia] oil, the aqueous distillate of the bleached drug smelled of sulphur dioxide 



*) BuU. Imp. Inst 18 (1920), 338. — •) It is not said how the determination was carried out. — ») United 
States Commercial Reports 1921. As per Journ. Soc. Chenu Ind. 40 (1921) R. 235. — *) Recueil Trav. Chim. Pays- 
Bas et Bdgique 87 (1918), 355. As per Angew. Botanik 3 '(1921), 107. — •) According to the Index Kewensia 
GoUtis amhoinisns is identical with C aromaticuSf Benth. — •) Journ. Assoc. Off. Ag^-ic. Chem. 41 (1921), 422. As 
per Journ. Sloe. (Item. Soc. 40 (1921), A. 488. — ') Comp. also Gildemeister and Hoffmann, The Volatile 
(His, 2"" edition, vol. II, pa^e 620. — •) Journ. Amei-ic. Phartn. Assoc. 10 (1921), 453.' 



Commercial and scientific notes on essential oils. 27 



1 



and contained no oil at all. Even upon cohobation of the aqueous distillates no oil 
was obtained. The distillate, however, then had a very pleasant odour. 

The hitherto undecided question, whether bleached coriander is, found on the - 
market, could therefore, it seems, be solved with the aid of distillation. As far as 
our own experience with drugs goes, we have only found bleached hops and orris 
root,' which of course were unfit for distillation. 

Oil of Cestui Roots. — In 1916/17 the Kashmir State Forest Department realized 
Rs. 3V* lakhs revenue from the export of costus roots, 4.524 maunds of 82 lbs.' being 
marketed*). 

Cubeb OiK — A sample of this oil was examined by C. T. 3ennett*) and was 
found to lack the characteristic taste and odour usually associated with this oil. 
The physical characters answered the requirements of the' British Pharmacopoeia 
(d 0.922; « — 38°; n^^o 1.4965; 75 per cent, distilled between 250 and 280°). On adding 
a few drops of nitric acid tOra solution in glacial acetic acid, the oil gave a distinct 
violet coloration, as is the case with oils containing gurjun balsam oil. On fractionation, 
the lower-boiling fractions showed a higher optical rotation than usually observed, 
the higher-boiling portions, however, which gave the gurjun balsam reaction, had 
a lower and more normal rotation. Further investigation revealed that the oil had 
been distilled apparently from genuine, but sitiall and immature fruits of Tiper CvUbeha, 
whilst the Ph. Brit. rec(Uires that only fully-grown fruits should be employed. 

Curcuma Oik — From this oil, d^ 0.9692, djoo + 0° 21' (in a 25 mm. tube), S. V. Hin- i 
tikka^) obtained, on boiling with sodium ethylate, and after repeated distillation a pale 
yellow oil turning rapidly dark (b. p. 110 to 115° [8 mm,]) which on treatment with 
hydrochloric acid and washing with water boiled at 115 to 116° (l6 mm.); d^O.9481; 
no 1.50543. From this product, two semicarbazones were obtained, m. p. 129° and 
153 to 154°, which furnished the following ketones:— a) b. p. 116 to 118° (10 mm.), 
d^ 0.9493, «2oo+80 30' (25 mm. tube), n^ 1.50177; oxim^, b.p. 160 to 161° (15 mm.); 



h) b. p. 122 to 124° (15 mm.), d^0,9479, d,oo + 6^40' (25 mm. tube), nDl.49951. Since 
the letter ketone yielded, on treatment with semicarbazide, semicarbazones, m. p. 153 to 
154° and principally with m. p. 125°, the .two ketones were considered to be identical. 
The difference in the constants of the ketone are explained by its great tendency to oxidize. 
The combustion of both semicarbazones pointed to the formula CioHisO of the ketone. 
On oxidizing the crude ketone (not treated with hydrochloric acid) with potassium 
permanganate the author obtained a ketone (semicarbazone, m. p. 203 to 204°) which 
appeared to be identical with Rupe's^) ^tolylmethylketone, in addition to a substance 
\yhich, on heating beyond 300°, was decomposed without previous melting (terephthalic 
acid?). When treated with a hypobromite, the ketone yielded a small quantity of a 
body melting at 33 to 34° (curcumic acid?). . 

Crigeron Oil. — The abundant occurrence of Erigeron canadensis, L, in the 
neighbourhood of Miltitz induced us to distil this well-known weed. 

The whole plant, when just beginning to flower, yielded 0.264 per cent, of oil of 
the following constants: d^o 0.8720, aD + 53°56', nDwo 1-49922, acid v. 0.3, ester v. 
about 63.5 (the change of colour when titrating was rather indistinct), ester v. after 
acetylation 70.3, soluble in 5.5 vols, and more of alcohol of 90 percent. 



1) Perfum. Record 12 (1921), 51. — *) Per/um. Record 12 (1921), 90. — ») Zur Kmntnis des Cureumaols I. 
Helsingfors 11>21. — *) Comp. Report April 1911, 57, 






28 



Report of Schimmel S Co. 1922. 



!&.!<■.•■ 



f 



^'. 



rf<;. 



The herb without roots, but flowering more abundantly, yielded about the same 
quantity of oil (0.26 per cent). It was a little heavier and seemed to be strongly 
predisposed for resiniflcation: duo 0.8836, «© -f-50°4', nD»o 1.50624, acid v. 0.3, ester v. 
about 70.9 (see above), ester v. after acet. about 81.9, soluble in 4 vols, and more of 
90 percent, alcohol with slight turbidity. 

Both oils were brownish yellow and smelled feebly aromatic. When diluted their 
odour somewhat resembled that of neroly. No similarity with caraway, however, 
noticed with oils previously distilled^), could be stated. 

■ 

Essential Oils^ Sicilian and Calabrian. 

The exports from the chief shipping place Messina in 1921 presented the following 
aspect: — 



Destination 



Argentina . 
Austria . . 
Belgium 
Canada . . 
Denmark . 
Egypt . . 
Australia . 
France . . 
Germany . 
japan . . 
Great Britain 
British India 
Dutch Indies 
Norway . . 
Holland . 
Rumania . 
U. S. A. . 



Lemon oil 
Kilos net' 



Bergamotoil I Orange oil Mandarin oil 1 

I i 

Kilos net Kilos net : Kilos net 



Other 
Citrus oils 

Kilos net 



Sweden 

Spain 

Switzerland . . . 
Uruguay .... 
Czecho-Slovakia 

Turkey 

Bulgaria .... 
Portugal .... 
British South Africa 
Greece 



3197 

188 

1119 

3517 

2264 

675 

20271 

15465 

28571 

462 

110714 

658 

100 

600 

6485 

239317 
645 
2728 
211 
455 
524 

25 
120 
300 
210 



776 
.116 
396 
246 
540 

407 

6830 

9078 

1516 

10460 

130 

100 

2125 

77 

16364 

545 

810 

130 
100 
112 



97 

50 

293 

509 
10 

146 
3335 
8629 

14174 
106 



4188 

50 

31049 

285 

158 

90 
278 



60 



202 
71 

441 



32 

48 
60 



58 



22 



53 



10 



Total kilos net 438821 



50880 1 63500 



772 



210 



Altogether kilos net 554183.— 

. against „ „ 569744.— in 1920. 



*) Comp. Gildemeister and Hoffmann, The VolatiU Oils, 2"** cd., vol. Ill, p. 604. 



Commercial and scientific notes on essential oils. 



29 



orts were 


distri 


bu 


ted ovei 


' the 


various months 


as specified hereafter: — 






1920 


1921 


January . . . . kos gross 


98851.— 


66865.- 


February 


9 • 




« 


ti 


81 735.— 


173851.- 


March . 


• • 




n 


n 


102096.- 


105497.— 


April . 


> • 1 




M 


n 


67280.- 


108987.— 


May . . 


• « 




» 


n 


50533.— 


70009.— 


June , . 


» • « 




n 


n 


53348.— 


85988:— 


July . . 


• • 




n 


n 


53102.— 


48397.— 


Augqst . 


• a 




n 


n 


41332.— 


27310.— 


September . . 




if 


n 


45015.— 


49214.—. 


October . . . 




it 


n 


76721.— 


51 198.— 


November . . 




n 


n 


142904.— 


44691.— 


December . . 




n 


If 


133133.- 


72868.- 




kos 


gross 


. 946050.-*) 


904875.-*) 



Average prices in 1921. 

The prices are understood in Italian Lire for 1 Sicilian pound of 317 grams. 



Month 



Lemon oil 



Bergamot oil 



Orange oil, 
sweet 



Orange oil/ 
bitter 



Mandarin oil 



January: 



M 



»l 



»» 



3»-d to 

10th 

17th 
24th 



» 



i» 



February: 



n 

n 



March : 



»» 



»» 



n 



April: 



w 



l» 



» 



May: 






1st 

7th 
14th 
2lst 

1st 

7th 
14th 
21st 

2nd 

nth 

18th 
25th 

2nd 
9th 

16th 
23rd 



n 

n 
»» 
n 
n 

n 
n 
n 
)) 

n 
n 
n 
n 

n 
n 

n 
>i 



une 



n 
n 
n 



6th „ 
13th- „ 
18th .^ 



8th 
15th 
22nd 
31 St 

5th 
12th 
19th 

26th 
5th 

12th 

19th 
31 St 

9th 
16th 

23»-d 
30th 

7th 

14th 
21 St 

31 «t 

4th 

11th 
18th 
30th 



11.75 
11.75 
11.— 
10.— 

9.50 
9.50 
9.50 
9.25 

8.50 
a50 
8.50 
8.25 

7.— 
6.50 
6.— 
5.75 

5.50 
5.25 
5.25 
5.50 

5.80 
5.80 
6.- 
7.- 



82.— 
81.- 
80.— 
79.- 

77.- 
77.— 
77.- 
75.— 

73.- 
72.— 

70.- 
69.— 

66.50 
68.— 
68.- 
66.— 

64.- 
62.- 
60.— 
58.— 

50.- 
50.— 
54.— 
55.— 



46.— 
46.- 
45.— 
44.— 

43.— 
43.— 
43.— 
42.50 

41.— 
40.— 
40.- 
40.— 

34.— 
34.— 



35.- 
34.— 
32.— 
31.- 

32.- 
32.— 
32.— 
31.- 

30.— 
28.— 
28.- 
28.- 

i24. — 
23.— 



33.— 


23.- 


33.— 


23.— 


31.50 


22.— 


31.- 


22.— 1 


30.— 


21. 


28.- 


20.- 


23.— 


17.— 


20.- 


17.- 




26.- 



100.- 
95.— 
95.- 
93.- 

90,- 
85.— 
85.— 
83.— 

80.- 
78.- 
78.- 

78.— 

70.- 
67.— 
55.- 
55.— 

50.- 
50.— 
45.— 
45.— 

40.— 
45.— 
45.— 
50.— 



^) The net weight is arrived at by deducting 40 per cent. 



Report of Schimmel fi Co, 1922. 





Month 




u™.™., 


Ikrl>n»tOi 


; OranKt oil, 
1 iwect 


Oranae oil. 
biller 


Mandarln oil 


)ulV: 


!•< 


, 9ih 


7.75 


K.— 


3*;- 


26.~ 


50.— 




nth 


„ 16'h 


7.75 


53.- 


1 32.- 


26.— 


■ 50.- 


„ 


ISth 


„ 23"i 


7.25 


53.- 


j 31.— 


27.- 


59.- 


„ 


25th 


, 36th 


7.75 


i 55.50 


35.- 


28.- 


62:- 



22"'' ,, 
September: 1*' „ 



24"' , 
November: 2"'' „ 



, 24"' I 
, 30th 



, iS'h 

, 22"'' 



8.50 ton. 

10.50 
9.75toll. 



a50 
8.30 

7.75 
7.50 



48.- 
46.- ■ 

48.- 



26ih „ 31" 



7.75 
7.50 



3.50 



60.- 



.- 


3150 


__ 


3X50 


.— 


34.- 


.— 


34.- 


.50 


32.- 


.— 


31.- 



55.- 



Bergamot Oil. ~ After a short period o1 comparative firmness towai^s tlie end of 
April last year, the market relapsed into the old dull state, so that the prices sank 
nearly 20 percent. 'Attempts made from certain quarters to monopolize the market, 
failed. Only in the course of the month of August, a sudden change took place, 
owing to a vivid demand from all foreign countries, which coincided with the purchases 
speculators had to make in order to cover their engagements. However, there was a 
noticeable downward tendency again already in the following two months, as the coming 
new crop induced various producers to put their stocks on the market. The yield of 
last year's autumn pressing is somewhat lower than the previous one, but in con- 
sequence of lack of transactions the position of the article continues weak. One may 
there 



Commercial and scientific notes on essential oils. 31 

. ester content and defective solubility, most of the products now dealt with showed 
almost normah constants : The specific gravity is generally in proportion with the ester 
content (there are no exact indications), « -(- 12 to + 22° (on an average ■+• 16 to + 17°), 
soluble in 80 and 82.5 per cent, alcohol, ester content 31 to 36 per cent, for the oil 
prepared in Movember/December and 36 to 39 per cent, for that obtained m fanuary/ 
February. In some regions, the optical rotation of the oils was a + 28 to 31°. 

It results from these constants, as the author remarks, that the effects of the 
drought in summer 1920 is less noticeable in. the quality of this year's product than 
in that of last year's crop, but there is not a similar improvement in the yield. The 
quantity expected is only 70 to 75000 kilos, i.e. less than half a normal crop. 

"With regard to the remarks which we connected with our discussion of Parrozani's 
publication on bergamot oil of the 1920/21 crop (our last Berichf, p. 20), the author points 
out that the constants established by him"^ do not refer to the oils from fallings but 
to those of ripe fruits. He further states that the samples have always been collected 
by officials of the stations in the various producing districts, who also watched the 
manufacturing process. The high rotatory power of the oils (« up to +37°) was 
easily explained by that of the terpenes contained therein (« up to +72°). There 
could not be any suspicion of adulteration with lemon or' orange oils. Besides, his 
figures were not intended to be a firm criterion for bergamot oils, but meant to show 
that absolutely pure oils may sometimes haVe abnormal constants. 

Lemon Oil.— The downward tendency, of which we reported k year ago, lasted 
until May, when such a low price level was reached that all concerned in the lemon 
oil trade had to sustain the most serious losses. A fairly brisk demand which then 
arose, sent the prices up a little, but only for a very short time, as the rumours of l>ad 
prospects for the next crop proved to be exaggerated. Even a vivid demand, especially 
from the United States, in the course of September, only led to a very moderate 
hardening of the market, and although the October shipments were twice as large as 
those of the previous month, no considerable rise was caused, as the imminent new 
crop induced the producers to come forth with their stocks. The yield was normal 
and taking into consideration the quantities still available of the old crop, it is thought 
that a further decline of the prices may be predicted, as speculative attempts to bring 
about a change have always only had a temporary effect. Only if the chief places 
of consumption showed a much keener interest in the article, conditions might alter. 

Sicily supplies 88 per cent, of the total Italian lemon crop, whereas Calabria only 
contributes 4, Campania 3.5, Apulia and Liguria 2 each and Sardinia 0.5 per cent.^). 
Most of the fruits are exported, only part being used for the manufacture of the 
essential oil. In Palermo 90 per cent., in Siracusa 60 per cent and in Catania 40 per cent 
of all the Citrus trees grown are lemon trees. The varieties cultivated most are those 
producing oval fruits with a thin and smooth ^kin. Good lemons are supposed to 
have pale yellow skin without any excrescences, sour juice and few pippins. In 
Sicily, the following classification is made according to the time of gathering: — 
A) Marzioli or Massani. They ripen in December, provided that favourable weather 
immediately after the normal crop, i. e. in March, produces another bloom. B) Lemons. 
They are the fruits of the normal bloom in April and Mi^y, ripening from December 
to February and being collected during these months. C) Biancucd or Bianchetti, also 



») H. C. Holtz, Chem. Weekhlad 18 (1921), 108. 



32 Report of Schimmel a Co. 1922. 

called Sicioppi. These ripen after the normal crop and come from June blossoms., 
D) VerdeUi. They are summer fruits, forced to premature ripening by a special process. 
The trees are left dry until the end of )uly, but then watered profusely. This causes 
an abundant bloom in August and September, so that the still greenish fruits can 
already be gathered in the following summer. Although this proceeding shortens the 
life of Ihe trees from 80 to 40 or 50 years, the yield of Verddli offers ample com- 
pensation for this disadvantage. E) Bastardi or Bastardoni. These are the names of 
the belated fruits of the VerdeUi crop, gathered in August. It is said that the rotatory 
power of the oil from Baatardoni and Bianehe.tti is not higher than 5i°'). 

For the manufacture of the essential oil, only such lemons are used, the abnormal 
size or form or other undesirable qualities of which make them unfit for being ex- 
ported. These rejected fruits amount to about 25 per cent, in the Palermo and Siracusa 
districts, whereas in those of Messina and Catania they may come up sometimes to 
75 or even 80 per cent, of the crop. 

According to De Salvo, 63000 lemons yield 100 Sicilian pounds = 32 Ifilos of 
oil. The same as with the bergamots, more and better oil is obtained from green 
than from ripe fruits, in consequence, the lemons gathered from December to February 
are to be preferred. The lemons growing near the coast of Amalfi (Campania), for instance, 
which ripen very late (in summer), contain so little oil that is does not pay to obtain it 

Messina is the most important Sicilian export harbour for lemon oil, although a 
certain part goes from Catania and Siracusa. Reggio is the centre for the oils produced 
in Calabria. 

Of the various methods of determining the citral content, Holtz considers to be 
the best those of Walter and Bennett (with hydroxylamine)^), Neber (with phenyl- 
hydrazine) and Romeo (with neutral and acid sodium sulphite). The last-named method, 
by means of which according to Bert^ and Patan£°) a citral content of 4 to 5.6 per cent. 
is found for good lemon oils, is used in the laboratory of the Messina Chamber of 
Commerce, Patan^ thinks') that far too much value is attached in commerce to the 
citral content, which ought not to be less than 4 percent."). The aroma of the oil 
depends on other constituents, present in small quantities and which do not come 
into consideration for the usual chemical analysis. The lemon oils of the finest aroma, 
>. e. those of the fiovember/December crop, contain less citral than the inferior 
qualities of February/March. 

Orange Oil, bitter. —The lowest price level was reached tow; 
June, with 17 Lire, until in the middle of )uly the general rise of 
also affected this article. The climax was 50 Lire, end of Septemb 
October the price had gone down again to 34 Lire. The new crop h 
as there are old stocks from 1920 one may reckon with a continue 
for the next months. 

Orange Oil, sweet. — The price, which in March 1921 was stil 
one half of it towards the middle of June, hardened gradually duri 
jijly and August, reaching its highest stage end of the latter month 

■) According to other observations, -4-54" Is the lowcBl limit, down Id which tl: 
to. Comp. Cildemeisler and HoHmann, Tht Valatile Oils, 2"' edition, vol. Ill, p. 17. — 
melhod is to be prelerred, although the figures arrived at are 10 per cent, too low, rei 
citral present. Comp. £ei,^l October 1909, 154. — 'i Biv.ltal.EaetnteeI'rof.m9,l.,p. 
— ') Coup. B€i>ort April 1914, 5S. 



Commercial and scientific notes on essential oils. 33 

This rise was chiefly due to the vivid demand from abroad, but it was accentuated 
by the supposition that the lasting rain would seriously damage the blossom. Besides, 
speculative purchases were made to a very great extent, with a view to force the 
article into an upward movement. This scheme did, not succeed, however, owing to 
the buyers* refusal to pay the high prices demanded and to the approaching new crop. 
A firmer tendency, noticed in March, was only temporary, and at present the article 
is rather neglected, the same as the other Citrus oils. 

According to official statistics^), the Italian orange crop originated as follows: — 
Sicily 57 per cent, Calabria 20 per cent., Campania 16 per cent., Apulia 3 per cent, Li- 
guria 0.7 per cent., other districts 3.3 per cent. Only second-rate fruits are used for 
manufacturing the oil, 70000 oranges being required for producing 100 Sicilian pounds, 
equal to about 70 English pounds. According to the statistics of the Exchequer, the 
exports of bitter and sweet orange oils were as follows:— 

1917 . . . . 72347 kos to the value of 2532145 Lire 

1918 .... 49109 „ „ n n n 1964360 „ 

1919 . . . . 103913 „ „ „ „ „ 4156520 „ 

France, the United States and England were the principal importers. 

In 1919, Jamaica exported 168415 lbs. of orange oil. According to an English 
periodical*), this large shipment was due to the exceptionally good price obtainable 
for the oil. Jamaica's capacity for orange production is nearly a milfion boxes at 
present Within ten years this output might be doubled, if she could obtain a regular 
profitable market ^ But the jsrohibitive U. S. A. tariff against Jamaican fruit and restricted 
shipping to the United Kingdom held back orange cultivation. The Jamaica Agricultural 
Society is urging the Government of the Island to make further representati6ns to the 
Canadian Government for a preferential duty on West Indian fruit This the Canadian 
Government have so far declined to do, alleging that the British West Indies can only 
supply a small portion of the amount required. Jamaica replies that, given such 
encouragement, there would at once be a responsive effort in making her neglected 
trees more productive, and new plantations would be engaged in, for certain districts 
in the island have such conditions as make orange cultivation their best industry. 

P.Mirgodin'') describes a sorcalled **new*' machine, constructed by the "Ecuelles Ltd.** 
and invented* by two West Jndian planters, with the aid of which the essential oil can 
be obtained from the various citrus fruits. He states that from 0.5 to 1 oz. of lemon 
oil and 2 to 3 ozs. of orange oil or oil of limes can be got from one bushel of fruits. 
The machine is constructed in three different sizes. It results from Mirgodin's description 
that the peeling proceiss, described years ago by Hood and discussed by us*) is here 
referred to. 

A disease which occurs in most citrus-growing countries and is fairly prevalent 
in Australia, the so-called collar rot^), often escapes the notice of the growers until 
serious danfage has been done. Its appearance and treatment are described in Agric 
Gaz., New South Wales (1920, 31 , 439). Collar rot manifests itself most frequently by 
"gumming" on the trunk just above or close to the ground. In many cases the bark 
in the vicinity is dry and brittle. In young trees the leaves show "yellowing", or 
chlorosis, especially on terminal twigs, but in older trees chlorosis may not develop 



*) H. C. Holtz, Chem. WeeTchlad 18 (1921), 108. — «) Perfum, Becord 12 (1921), 184. — «) Patfim. modeme 
14,(1921), 257. — *) Comp. Bericht (German) 1920, 32. — ») Bull. Imp. Inst. IS (1920), 437. 

3 



34 Report of Schimmel 5 Co. 1922. 

until the attack has reached an advanced stage, when the tree has been nearly ring- 
barked. Associated with the disease^), a fungus parasite (Fusarium limonis) is con- 
stantly found, which enters the tree at an injured part, -goes very slowly through the 
tissues of the trunk, and if left unchecked accomplishes the ring-barking of the tree. 
The treatment recommended when "gumming*' has been observed is to scrape the 
earth away from the base- of the tree, remove the dried bark apparently infected by 
the fungus, and paint the wound with a bluestone paste composed of IV^ lbs. of 
copper sulphate, 4 lbs. of unslaked lime and IV* gallons of water. Where collar rot 
is too far advanced for the tree to be saved by this treatment it should be removed 
and burned, and the stumprhole limed. Bad drainage is conducive to this disease. 



Estragon Root Qil.— Estragon roots, collected in Miltitz, yielded on distillation 
with steam 0.21 per cent, of a dark brown oil. The feeble smell recalled somewhat 
that of radishes and was, in any case, entirely different from that of the herb: — 
diBo 0.9744, n^MO 1.56406, acid v. 2.1, ester v. 14.4, soluble in 5 vol* of 90 per cent, 
alcohol with turbidity, which gradually diminishes on further dilution. Owing to the 
dark colour, it was impossible to determine the optical rotation. 

Eucalyptus OIL — As per an American report^), the eucalyptus oil industry in 
Victoria appears to be in a very low condition, many of the distillers having ceased 
to work. In the iVlaryborough district, only one distillery is at work. In the Neilborough 
district, about half the factories are working, but only at low-grade oils. 

4 

In a communication dealing with piperitone, J. Read and H. G. Smith ^) furnish 
some details concerning the history of the "peppermint" eucalypts of Australia. 

Soon after the arrival of Governor Phillip in Mew South Wales, in 1788, a species 
of this peppermint type> growing plentifully in the neighbourhood of Port Jackson 
attracted the attention of the colonists, and the first eucalyptus oil to be distilled was 
obtained from its foliage and employed for medicinal purposes by Surgeon-General 
Dr. White, who gave the plant the name Peppermfnt Tree on account of the very great 
resemblance between the essential oil drawn from its leaves and that obtained from 
the peppermint in England. The oil was found by Dr. White to be mudi more effi- 
cacious in removing all cholicky complaints than the English peppermint oil. Nowadays, 
the tree is known to have been Eucalyptus piperita, which is common in the Sydney 
district and the Blue Mountain Ranges of New South Wales*). 

The eucalypts^ of the "peppermint*' group are now known ^) to contain piperitone 
CioHieO (p-menthenone-3), occurring, with the exception of E. apiculata, in association 
with ^,a-phellandrene and, in most cases, also with the corresponding secondary alcohol 
piperitol. When isolated in the usual way, by fractional distillation under atmospheric 
pressure followed by treatment with sodium hydrogen sulphite solution, thei piperitone, 
on regeneration, undergoes racemisation and usually exhibits a feeble lasvoratation not 
exceeding [«]— 1°. Read and Smith ascribe this to the possible presence of small 
quantities of the laevorotatory aldehyde "cryptal". By conducting the distillations. 



') According to the description the so-called "gumming" disease (gummoaisjj which may attack all sorts 
of citrus-trees, seems to be referred to. Comp. Bericht (German) 1921, 89. '- ') Americ. Perfiim. 16 (1922), 318. 
— 8) joum. chem. Soc. 117 (1921),"779. — *) Comp. Gildemeister and Hoffmann, The Volatile Oils, 2^^ edition, 
vol. Ill, p, 277. — ») Ibidem, p. 283. 



V 



Commercial and scientific notes on essential oils. 35 

however, under greatly diminished pressure it is possible to isolate- the piperitone in 
its natural, markedly laevorotatory form ([a]© — 42.8^*). 

A specimen of piperitone obtained by Read and Smith from the essential oil of 
Eucalyptus dives by distillation under atniospheric pressure and by purification by 
means of neutral sodium sulphite, showed the constants:— b. p. 128.5^ (25 mm.), 
[ajp— 0.27^, nojoo 1.4843; hydroxylamino-oxime, m. p. 169. to 170°; oxime, m. p. 110 to 
111°; semicarbazone, m. p. 219 ta 220°. (The semi carbazone prepared by Wallach^) 
.from J*-29-menthen1one-3 h^d the m. p. 224 to 226°.) On treating piperitone with benz- 
aldehyde in presence of metallic sodium the authors obtained benzylidene^^Z-piperitone 
CioHuO : CH • CeHg, m. p. 61°; oxime, m. p. 130 to 131°. 

The bimolecular ketone CgoHg^O^ from piperitone obtained by 3aker and Smithy 
under the identical conditions, yielded no benzylidene compound. 

From the oil of Eucalyptus hemiphloia, R. T. Baker and H. G. Smith ') succeeded in 
obtaining a new crystallised phenol which .they termed australol. This phenol, which 
occurs also in other oils of the "Boxes*', was prepared in the same manner as tasmanol 
(comp. Report 1916, 30) and showed the following constants: — m. p. 62°, b. p. 115 to 
116° (10 mm.), dgoo 0.9971, «d±0, nowo 1.5195, mol. refr. found 41.50; calculated for 
three double bonds 41.74; benzoate, m. p. 72 to 73°. In alcoholic solution, ferric 
P rvu chloride gave with the phenol a fleeting greenish yellow colour 

>^\ at first, quickly changing to bright yellow. The odour of australol 

HC |CHa reminded of ordinary phenol, and the skirt was attacked by the 

jjp |p|j new phenol in exactly the same manner as by phenol. Combustion 

N^/ and molecular weight deterrnination proved the empirical formula 

C-CH2-CH:CH8 C9H12O. Since the unsaturated phenol gave no colour reaction 

Probable structure with picrfc acid, the unsaturated side-chain has most probably 

of australol. . V. . . ,.,«,.. ... 

the atlyl grouping, two double bonds thus occurring m the 
nucleus. The authors conclude, therefore, that australol is a dihydro-^allylphenol 
of the structure given above. 

From the oil pf Eucalyptus hemiphloia and related eucalypts. Baker and Smith 
obtained formerly*) an aldehydic body which they termed aromadendral. Recently*) 
it was found that this body, which occurs likewise in the oils of the "Box** and "Mallee'* 
group, was no uniform substance, but a mixture of aromadendral proper, CioHuO, with 
cuminal CioHiaO, phellandral CioHwO and a new aldehyde "cryptal" CioHieO. The 
latter aldehyde had escaped the authors in their first investigation, because it did 
not form a solid compound with sodium bisulphite, and the liquid combination is not 
decomposed by sodium carbonate. These very properties afforded later on a satis- 
factory method for the preparation of the new aldehyde. According to a method 
given in detail, the authors succeeded in isolating, as they, believe, pure cryptal from 
the oils of Eucalyptus hemiphloia and E. polyhractea. However, the constants of both 
aldehydes do not agree with each. other ^. 

Cryptal from the oil of E, hemiphloia:— b, p. 99 to 100° (10 mm.), 221° (760 mm.), 
daoo 0.9431,. «D —76.02°, nDa,o 1.4830; semicarbazone m. p. 176 to 177°; oxime and 
hydrazone were liquid. 



s. 



1) Comp. Bericht 1921, 24. — «) LieUg's Annalen 362 (1908), 272. — •) Baker and Smith, A Research 
on the Eucalypts and Their Essential Oils, 2"" edition 1»20, p. 396. — *) Comp. Reports April 1901, 34; October 
1901, 29. — *) Baker and Smith, A Research on the Eucalypts and Their Essential Oils, 2"«* edition, 1920, p. 383. 
— •) 146 explanation is given for this discrepancy. 

3* 






36 Report of Schjmmel S Co. 1922. 

Cryptal from the oil of E, polyhractea :—dioo 0.9443, Od ~49.7^, nD»o 1.4849; semi- 
carbazone, m. p. 180°; oxime and hydrazone were liquid. 

Attempts to separate aromadendral CioHuO from the other aldehydes present in 
the oil in the pure state, were hitherto without success, cuminal being mostly present. 

Oil of the Bark of Eucalyptus Macarthuri. — From the ground bark of E, Macarthurif 
Deaiie et Maiden, a species cultivated on a large scale near Emerald, Victoria, Baker 
and Smith ^y obtained by steam-distillation 0.12 per cent, oil of a light amber colour 
and a distinct odour of geranyl acetate. Three different samples of this oil showed 
the following constants: — dwo 0.9099 to 0.9218, 00 + 1.2 to + 1.40, ni>»o 1.4648 to 1.4718, 
soluble in 1.2 vols, of 70 percent, alcohol, ester v. 169.5 to 195, equal to 59.2 to 68.2 per cent, 
geranyl acetate; ester v. after acet. 198.8 to 224, equal to 69.6 to 78.4 per cent, ester. 

The optical rotation of the oil is ascribed to the presence of a small quantity of 
d-pinene. Eudesmol, a constant constituent of the leaf oil from Eucalyptus Macarthuri, 
does not appear to be present in the bark oil. Apart from this, the constants of both 
oils appear to be fairly identical. 

Fennel Oil. — Our industry has not seen much of the good yield of last fennel 
crop, as the largest share by far was sent abroad, where higher prices were obtainable. 
Even the factories situated in the vfcinity of Lutzen fennel districts did not succeed in 
buying fair quantities. It would have been better if the Government had taken the 
suggested measures for stopping the export, or at least restrict it, so that the work 
connected with the distillation of the fennel seeds remained in the country. It is to 
be hoped that something will be done with regard to the next crop, a$ otherwise the 
distillation of fennel oil will pass entirely out of the hands of the German industry. 

C. E. Sage*) examined two fennel oils of Spanish origin and known to have been 
prepared from the entire plant of Foeniculum mdgare. The following constants, found 
by him, seem to indicate that the products in question were at least partly composed 
of bitter fennel oil: — dicBo 0.9203, and 0.9340, «!>-[- 46 o and + 24 o, npaso 1.4945 and 1.4980, 
soluble in 1 vol. of 90 per cent, alcohol, congealing point ... no indication at — 15°. 

Frankincense Oil. — By fractionated distillation of 1 kilo of terpeneless oil of 
frankincense^) in a vacuum, E. Fromm and R. Klein*) obtained a body CibHigO, b. p. 117 
to 1190 (22 mm.), 210 to 211° (ordinary pressure), diso 0.9504. This compound, called 
«-olibanol by the authors, was not identical with the olibanol prepared by Fromm and 
Autin*^), also from oil of frankincense, as it did not yield any pinonic acid on oxidation 
with potassium permanganate. The olibanol that yielded pinonic acid could be obtained, 
however, if the oil of frankincense or the product of the distillation were distilled under 
ordinary pressure. There are in consequence two olibanols; viz., a-olibanol, as found 
in the natural oil of frankincense, and /^-olibanol, formed through a re-arrangement of 
the molecules on heating the former above its boiling point. As a-olibanol does not 
yield any pinonic acid, it is neither identical with verbenol, nor with dihydroverbenone. 
On reducing o-olibanol with sodium and alcohol, dihydro-olibanol is formed, CioHisO 
(b. p. 100 to 102° [25 mm.], o-nitrobenzoate, m. p. 135 to 137°), which is not identical 
with dihydro-verbenol. 



*) A Besearch on the Eucalypta and Their Essential Oils, 2"** edition 1920, p. 318. — *) PerfUm. Record 
12 (1921), 46. — «) Cf. page 142 of this BepoH. — *) Liebigs Annalen 426 (1921), 213. — ») Cf. RepoH 
April 1914, 63. 



Commercial and scientific notes, on essential oils. 37 

When tryipg to reduce the j^-olibanol in the same way, the authors only obtained 
the unaltered' material, in addition to resinous products. 

An ordinary oil of frankincense, distilled in vacuo, yielded a compound CioHi«0 
(b. p. 1 14 to 1 16° [15 mm.], dwo 0.9502). This product (y-olibanol) which it was impossible 
to reduce like a-olibanol or to transform into the /^-compound by heating, yielded on 
oxidation a liquid acid and did not react with semicarbazide. Even after ordinary oil 

of frankincense had been stored for five years, no ^olibanol had formed in it. 

* ■ 

Geranium Oil. — The production of geranium oil in North Africa has decreased 
considerably. Whereas 140000 kilos were distilled in Morocco, Algiers and Tunis, in 
1914, only 15000 kilos were obtained in these three countries in 1920. In consequence, 
the price rose from 30 or 35 Francs in 1914 to 250 Francs per kilo in 1920. There 
was a change, however, in 1921, for in spite of a very small crop (only 14000 kilos) 
not more than 70 Francs were paid per kilo in the producing districts. As the geranium 
growers find these low prices unprofitable, they intend giving up the cultivation of the 
geranium plant altogether*). 

A. Rolet*) reports on the crops and the yield of geranium plants in various countries, 
where the plant is cultivated. The time of the crop varies according to the district 
and the way of cultivating. In the Provence, the crop takes place in August/September, 
very rarely for a second time in October/November, As the plants would freeze in 
winter, a fresh cultivation must be started every year. As soon as the leaves lose their 
lustre, the plants ^re mown, preferably towards evening on fine days, so that the herb 
does not dry out too much. 

In Corsica (Pelargonium odoratissimum), there are two cuts, in May and August, 
very seldom a third one in September/October, when only slips come into consideration*). 

In Algiers, the crop begins already in spring, generally in April, as soon as the 

plants start flowering. There is a second cut in )une/)uly and a third one in October- 

TSovember. There are five crops within two years, the yield being smaller in the first 

' year than later on. On good soil, such as in Boufarik, the stalks are from 50 to 70 cm. 

long, otherwise they only measure from .25 to 30 cm.*) 

In Italy (Pelargonium roseum, Willd.), there is only one crop in the first year of 
cultivation, in August/September, whereas in the second year the plants are cut in 
May, August and October/November. The plants can be used there for four, some- 
times even for up to eight years. If only the flowers are gathered, the oil of which 
is supposed to be finer, according to Blandini^), the crops are more frequent. The 
author once started on the 18**? of April in Portici and left off gathering the flowers 
on June 14*^, after having had eight crops. 

In Reunion, one crop follows the other ^). If the intention is to keep up the 
cultivation for several years, the plants are cut down more than if they are renewed 
every year. In order not to uproot the plants, tree-shears are used for cutting in the 
first year and sickles later on. The cut plants are sent at once to be distilled, for if 
they stay in heaps for some time they get hot, start fermenting and lose in value. 

The output varies and depends on all sorts of circumstances, such as way of 
cultivating, soil, manure, irrigation, number of crops, 2{c. 



1) Zeitschr. d. Deutsch. 01- u. Fett-Ind. 41 (1921), 825. — 2) Parfum. modcrne 18 (1920), 60. — ») Comp. 
RepoH October 1910, 70. — *) Comp. Report October 1918, 61. — ») Comp. Gildemeister and Hoffmann, 
The Volatile Oils, 2»<» edition, vol. II, p. 614, foot-note 5. Bepcyrt April 1907, 54. — «) Comp. Report 
April 1914, 64. 



38 Report of Schimmel S Co, 1922. 

In the Alpes Mari times in France, from 25 to 80000 kilos (on an average 40000 kilos) 
per hectare and year can be obtained on well irrigated, artifidally manured soil, if 
great care is taken of the plants. In the Var department, the yield may come up to 
75 and even IO060O kilos per hectare, according to L. Robertet. 

In Algeria the crops are estimated at from 25 to 27000 kilos per hectare. 

Blandini obtained from Pdargonium roseum, Willd., in Italy 26000 kilos of herb and 

3945 kilos of flowers per hectare. 

' • 

R. Knuth^) has published an extensive article on geranium oil (botany, distribution, 
cultivation and yield of the mother-plant and its varieties, chemistry of the oil and it^ 
components), with several good pictures' of Pelargonium species. The author thinks 
that the plants cultivated in the various countries may be considered either as varieties 
of cultivation or hybrids of other species, whose origin is now unknown or has been 
forgotten long since. In the beginning of the nineteenth century, there was a sort of 
fad to hybridize Pelargonium species, so that, for instance, the Geraniacece of Sweet*) 
(London 1820—1830) contain almost 500 of such artificial hybrids, whose origin already 
at that time had been partly unknown. In the course of time, the origin of each cross 
became more and more obscure, so that at the present time we are unable to determine 
te exact origin of a large part of the pelargoniums found in our botanical gardens. 
This is especially the case with regard to the species which were called lemon-geraniums 
as early as the time of Sweet, and with which the rose-geranium must be included*). 

Andrews*), in his Geraniums (1805), mentions a J^elargonium oxoniense^ closely 
related to Pelargonium graveolens and Pelargoni%m capitatum, which was first cultivated 
jn Oxford on account of its rose-ddour and sold under the name of Oxoniense roseum. 
Knuth thinks it very probable that the parent plant of the rose-geranium was originally 
purchased under the name of Oxoniense roseum and is related to Pelargonium oxoniense. 
Heuz6^) and Cordemoy'^) are mistaken in thinking that the species chiefly cultivated in 
Algeria and Reunion is Pelargonium capitatum, as the plant found there has leaves 
entirely different in shape from those of P. capitatum. This species rather belongs to 
the group of Pelargonium graveolens, L'Herit. 

It is probable that in France, in addition to rose-geranium, Pelargonium odoratissimum 
(L.), Ait. (belonging to the section of Peristera, according to Harvey) ancf Pelargonium 
fragrans, Willd. (a hybrid of Pelargonium odoratissimum and P. exstipulatum, L*Herit.) . 
are cultivated, though to a smaller extent. Both plants have a delicate texture and 
differ also in other ways from the rose-pelargonium. In Algeria and Reunion the two 
species are certainly not cultivated. 

The oil is furnished by the glands of the plant. These are found, as in all pelar- 
gonium species, in the green parts, especially on the surface of the leaves, where they 
are shorter than on the stem and the peduncles. In most cases they are from ^jis to 
V15 mm. long and can be seen with the naked eye. They consist of from one to three 
small cylindrical base cells and a small globular head, in which latter the oil is 
generally to be found When young, the end cell is colourless,, later on it is coloured 
by a yellow substance and finally becomes brown. The oil glands are of great use to 
the plant, as they protect it against insects and snails. As a matter of fact, all pelar- 
goniums are but little damaged by such enemies. 



1) Americ. Joum. Pharm. 93 (1921), 302. — ^) Died as a market-gardcncr in London. — ») Knuth 
calls ' 'rose-geranium" the chief parent plant of geranium oil. See lower down. — *) Herbalist in London, 
who published precious copper plates of foreign plants. — '^) Pelargonium oxoniensef van Eeden (Index 
Kewensia). — •) Bevue Horticole 65 (1893), 305. — *') Bevue Cult. Colon. 1904, 170. 



Commercial and sciENTinc notes on essential oils. 39 

BlandinFs assertion^) that the flowers produce a larger quantity of oil of excellent 
quality is in Knuth^s opinion certainly not in accordance with the facts. 

As to the geographical distribution of the plant, the author gives the following 
summary, many facts of which will be . known already irom our previous Reports, In 
France the plant was first cultivated near Crasse and at the foot of the Maritime Alps, 
near Cannes. Though it was known there as early as 1819, it seems to h^ve been 
grown only to a limited extent up to 1847. Shortly after that time, emigrants trans- 
mitted the cultivation to Algeria, where the plant was first grown in the district of 
Sahel, Western Algeria, between Oran and Mostaganem, afterwards in the plain of 
Metidja, near Algiers, and in the littoral of the province of Constantine, near Philippeville 
and Bougie. The cultivation did not spread to Reunion before 1880. It was favoured 
there by the sugar crisis of 1904—1906. — In the Spanish province of Granada, experimeTits 
regarding the cultivation of the plant Were made about 1890. Although the quality of 
the oil was excellent, the area of cultivation, producing from 600 to 1000 kilos annually, 
was not increased. — In the Jewish coiom'es of Asia Minor, Rischon-le-Zion and Petach- 
Tikway, there are plantations whidi were founded by Baron Rothschild. — The trial 
plantations of Pelargonium radula in Limaru, British East Africa, have not been 
continued, -r The author states that he has not been able to obtain information con- 
cerning the cultivation of the plant in Cbrsica. We would mention that it was introduced 
there from the Provence, about 1860, and quickly spread in the districts of Crbalunga, 
Sisco and Brando. v 

We have reported repeatedly on adulterations of geranium oil with citronella oil 
or fractions thereof^. It is often difficult to recognize such admixtures, as the constants 
are not always influenced sufficiently to become abnormal. Under these circumstances, 
a careful examination of the smell will rbqse suspicion, but only an exact chemical 
analysis can give absolute certainly. 

We had to deal with such a case quite recently, when a geranium oil was sent us 
for inspection from Spain. It behaved as follows: — diso 0.9002, «d —b^3S\ noMo 1.47171, 
acid V. 5.2, ester v. 50.8 = 21.4 per cent, ester, calculated as geranyl tiglinate, ester v. 
after acetylation 213.7 = 70 per cent, total geraniol, soluble in 2.3 vols, and more of 
70 per cent, alcohol, dilute solution slightly turbid. As the product was supposed to 
be a Bourbon oif, it struck us that the constants were abnormal in part, the specific 
gravity and the index of refraction being too high, the optical rotation too low. The 
sample therefcTre resembled rather an African distillate, but was suspicious in any case 
on account of its odour and defective solubility. It was proved through investigation 
that the oil contained an appreciable quantity of citronellal, a substance which is not 
a component of geranium oil. With the aid of bisulphite, several grams of citronellal 
were isolated out of 125 grams of the oil under examination and. identified by means 
of the semicarbazone, melting between 82 and 83°. A mixture with a sefnicarbazone 
prepared for ^he sake of comparison showed the same melting point, so that the identity 
of the two compounds is certain. 

In order to make quite sure, we treated 125 grams each of genuine pure Bourbon 
and African geranium oils in the same way with sodium bisulphite, when the quantities 
of aldehydic components obtained were so small that a chemical identification resulted 
impossible, whereas the smell seemed to indicate citral or a fatty aldehyde rather 
than citronellal. 



*) Bull, de VOff. du Gouv. de VAlgerie 12 (1906), 277. Comp. Gildemeister and Hoffmann, The Volatile Oils, 
2"" edition, vol. II, p. 614, foot-note 5. — *) Comp. Report 1917, 19 and Bericht (German) 1920, 36. 



40 Report op Schimmel S Co. 1922, 

On account of this result there can be no doubt that we had to deal with an 
adulteration. We presume that there was an admixture of citronella oil or a fraction 
thereof, which would explain the defective solubility. 

Gitigergrass Oil. — Two samples, described as sofia oil, were forwarded to the 
Imperial Institute from Dehra Dun in 1916. On investigation^), the oils revealed the 
following constants r — djH 0.9 10 and 0.907; od —150 48' and — 1403'; sol. in 2.1 and 
2.0 vols, of 70 per cent, alcohpl, no opalescence on dilution to 10 vols.; acid v. 2.3 and 
1.5; ester v. 25.7 and 19.8; ester v. after acet. 170.5 and 180.6. The oils showed a slight 
odeur of citral, the absorption test with sodium hydrogen sulphite, however, manifested 
nothing abnormal in this respect, since the two oils contained 12 and 11 per cent, of 
matter soluble in that reagent, whereas of a commercial oil 10 per cent, were absorbed. 

A further sample of the same oil originating from the United Provinces of India 
(1917) had the constants: — d^ 0.936; an + 42.87 O; nD»o 1.490; insol. in 70 per cent, 
alcohol; acid v. 4.5; ester v. 13.5; total alcohols, calculated as geraniol, 42.7 per cent. 

Oil of the Berries of Heeria paniculosa. — The berries of this anacardiacea^, 
indigenous in Zululand and known there as isifehu, yielded on water-and-steam-distillation 
4.47 to 6.07 per cent, essential oil^). The oil is located especially in the pericarp and 
shows no particular odour. It consisted for the greater part of terpenes and had the 
following constants:— d 0,832, « 3.75°*), acid v. 1.6, ester v. 4.2, ester v. after acet. 14.8. 

Oil of Houttuynia cordata.— By steam distillation of the herb Houttuynia cordata, 
Thunb., a piperacea known as Dohudame in Japan, Y. Shinosaki^) obtained 0.0049 per cent, 
of a light brown essential oil with a strong, somewhat disagreeable odour, and the 
following characters: — di60 0.8744; [a\^ — 5°; nDMo 1.4685; acid v. 16.65; sap. v. 28.40. 
On treatment with sodium bisulphite, methyl n-nonyl ketone (semicarbazone, m. p. 122 
to 123°) was isolated. Repeated distillation of the residual oil is yielded a terpene 
fraction, b. p. 60 to 61° (14 mm.), 167 to 168° (766 mm.), as the principal product; 
this consisted of an aliphatic terpene (probably myrcene) and a small quantity of a 
cyclic terpene. The oil also appears to contain a solid acid. 

Oil of Junipenis taxif olia. — From the leaves and twigs of Juniperus taxifoliaj 
Hook, et Arn. (Japanese shimamuroX a coniferous plant indigenous to the Ogasawara 
Islands, Y. Shiposaki^) obtained by distillation 0.24 per cent, of a light green oil. Two 
specimens of the oil had the following characters: — dig© 0.8675 and 0.8701; «!>—-? and 
— 29°; nij»oi.4702 and 1.4718; acid v. 0.94 and 0.0; sap. v. 11.69 and 10.37; sap. v. 
after acet. 19.60 and 18.89. The oil contained above 50 per cent, of a-pinene (mainly 
^^cupinene containing a small quantity of the (2,Z-a-isomeride) and possibly a bicyclic 
terpene, a free alcohol (CioHisO), ester, sesquiterpene, and sesquiterpene alcohol. 

Oil of Juniperus thurif era. — According to L. Lestra^), there is only a difference 
in the size and the build of the fruits between Juniperiis thurifera, var. gallica, De Coiny, 
growing wild in France, and Juniperus thurifera, L, occuring in Portugal, Spain and 



*) Bull. Imp. Inst. 18 (1921), 343. — •) This species is not mentioned in the Index Keivensia of 1910. 
— «) Chem. News 120 (1920), 277. Ace. to Bull. Moure-Bertrand Fils, April 1021, 135. — *) The direction 
of rotation is not quoted in the abstract. — •) Joum. chem. Ind. Japan 24 (1921), 557. Joum. Soc. chem. Ind. 40 
(1921), A. 560. — •) Journ. chem. Ind. Japan 24 (1921), 202. Joum. Soc. chem. Ind. 40 (1921), A. 411. — 
') Parfum. moderne 14 (1921), 210. 



Commercial and scientific notes on essential oils. 41 

North Africa. The plant is also easily distinguished from other Juniperus species^ 
like the very similar Juniperus Sabina, L, especially by the compactness and the 
shape of the sclerogen cells of the berries. After giving an exact botanical description 
of Juniperus thurifera, var. gallica^ De Coiny, Lestra reports on the essential oil 
obtained by steam distillation of the various parts of the fresh plant The yield 
amounted to 0.15 per cent, of a straw-coloured viscjld oil (0.096 per cent, of the dry 
plant). The constants were as follows: — diso 0.9115, ao+32.2o nowo 1.4963, soluble 
in chloroform and in 96 per cent, alcohol, in 20 parts of 70 per cent, alcohol, in 
10 parts of ligroin (?), acid v. 6.5, sap. v. 67.4, ester v. 60.9 (ester content 21 per cent., 
in addition to 0.57 per cent, of free alcohol), iodine v. 24.5. Through experiments 
with animals, it was established that the oil is an emmenagogue, like oil of savin. 

Lavender OiK — When last year's crop began, the market was very weak, for 
in consequente of the sluggish sales a considerable part of the previous campaign 
(it is rumored even about half) was still unsold in the South of France. The prices 
offered to the gatherers were low in consequence, only 20 to 30 Francs per 100 kilos 
of flowers being paid, according to the district. It is to be taken into account that 
the usual daily wages amount to 15 or even 17 Francs and that one man cannot gather 
more than 70 to 80 kilos per day. Mo wonder that the gatherers restricted their work 
to the more easily accessibly districts, i. e., the lower regions. This may account for 
the fact that, according to the unanimous judgment of our informants, the ester content 
of the oils was somewhat lower, on an average, than in the previous year, for the 
qualities with a high percentage are distilled exclusively of flowers from high regions. 
Owing to the low collectors* wages, only half the crop, which was very good last 
year, is said to have been gathered. At first, good lavender oils only fetched from 
55 to 60 Francs per kilo and there was very little demand. Only after the annual 
lavencfer oil fairs, the most important one of which took place at Digne on October 1*^ 
the market became firmer, as some Grasse firms purchased considerable quantities. 
Business resulted more brisk early in December, due to a fair demand from abroad, 
and towards the middle of January about 100 Francs hiad to be paid for good qualities 
of 40 per cent, ester. Then there was a pause and the market is quiet now with a 
slight downward tendency. If nothing unforeseen happens and the dernand continues 
slack, there may be a decline in the next months. However, it will scarcefy be con- 
siderable, as a good many owners mean to keep back their production, being con- 
vinced that the rising costs of gathering, distilling, etc., will influence the coming 
crop and send prices up. Besides, there is the possibility of smaller crop this time. 

According to a Bulletin du Syndicat des Produdeurs de Fleurs et d'Essence de 
Lavande du Departement de VaucluM et des Regions limitrophes, published in March this 
year and dealing specially with the fair at Digne on October 1st 1921, the normal 
prices for lavender oils ought to be between 90 and 120 Francs, if it is taken into 
consideration that the pre-war figures for medium qualities ranged from 30 to 40 Francs 
per kilo. The author tries to prove that the costs have trebled and that the selling 
prices ought to go up in proportion. The costs of gathering (from 4 to 7 Francs per 
100 kilos before the war) amounted to 25 Francs in 1919 and have sometimes exceeded 
50 Francs in 1920. Last year, the manufacturers declared that, owing to the general 
depression and the sluggish sales, they would rather take no flowers at all than pay 
more than 10 to 12 Francs. The gatherers knew this and some of them were willing 
to work nevertheless, but they were few in number. The owners of the lavender 
districts wanted more hands, however, and could only get them through paying higher 



\ 
\ 



42 Report of Schimmel S Co. 1922. 

. " ■ . •^■ 

wages. 25 Francs per 100 kilos had to be paid, but even then there were perhaps 

only 20 gatherers, where 200 were required. As the depopulation in the mountainous 

districts of Sault has reached about 20 per cent., as per the latest estimations, one 

will have to reckon with a shortage of labourers in the future. 

The costs of keeping the lavender plants in good condition and those of transport 
Of the flowers have likewise trebled. Up to 500 Francs have been paid for working 
1 hectare of wild lavender with 4 animals, a price which is out of all proportion, but 
if one takes it that in some districts only V* hectare can be worked daily by two 
men with four animals, a cost of 150 to 200 Francs per hectare would seem justified. 
The wages of labourers and drivers and the cost of the fodder have risen from 7 to 
25 and even 30 Francs in the mountains. The prices of the necessary implements 
have also trebled. 

The same is the case with the costs of distil^tion and the general expenses. An 
ordinary still holding 300 litres cost before the war from 400 to 500 Francs, whereas 
already some time ago from 1200 to 1800 Francs had to be paid. Coal has risen 
from 50 to 500 Francs per ton plus 200 to 250 Francs for transport. The wages of 
the stokers have trebled and the amount of work done has gone down. Taxes and 
other expenses have risen too and there does not seem to be ainy chance of reduction. 
• Finally it is stated that, contrary to the estimation of last year's crop at 150000 kilos, 
the total turnover on all the different fairs had not even reached 100000 kilos and 
that there was^ very little oil left in the hands of the distillers. 

A. Chiris^) reports, on the strength of his own investigations, on the differences 
presented by lavender oils obtained by open fire and by steam distillation. According 
to his ideas, the rotatory power of lavender oils distilled by open fire grows in ab- 
solute value with the ester contents. It is known*) that oils distilled by steam, under 
otherwise similar conditions generally contain a higher percentage of esters than those 
obtained by open fire. Chiris points out that a high ester content is not always a 
criterion for the quality of the oil. Of two oils, one distilled by open fire and having 
45i57 per cent, of esters, and. the other oil, steam-distilled, having 52.65 per cent, of 
esters, he preferred the former, as being superior in aroma. As regards solubility 
and density, lavender oils distilled by steam are less soluble in 70 per cent, alcohol 
(not soluble in 3 vols.)') and of greater density (d often more than 0.9) than oils distilled 
with water. As the indications of the United States Pharmacopceia (ninth edition) 
regarding density (d|^ 0.875 to 0.888) and solubility (soluble in 3 vols. 70 per cent, 
alcohol) are exact only for the latter kind of oils, it ought to be revised, as nowadays 
the majority of lavender oils are distilled by steam. 

In connection with the second Lavender Congress, held at Digne on October !«* 
last year, as mentioned before, Lautier Fils and Roure-Bertrand Fils published a paper 
each on lavender oil*). Lautier Fils tried to decide the question whether the quality 
of a lavender oil depends on its ester content. For this purpose, three samples of 
lavender grown in the same district. Saint Andre de Meouilles, were distUled under 
identical conditions;' vi-?., 100 kilos, of flowers, under a vapour pressure of 7 kilos, for 
45 minutes'^):— a) dry wild lavender, distilled 15 days after collection, b) fresh wild 



») Perfum. Becord 12 (1921), 404. — «) Comp. also our experiments, BepoH Apn\ 1907, 64. — ») These 
indications are not generally valid, as we have repeatedly distilled lavender oils by steam in the South of f ranee 
which dissolved in 3 vols, of 70 percent. alcohoK — *) Perfum. Becord 12 (1921), 342. — *) This indication 
is of no value, as the pressure sinks at once to that of the outer atmosphere, if the still is in connection 
with it through rising-tube and condenser. 



, '■ >■ 



Commercial and scientific notes on essential oils. 43 

lavender immediately after collection, c) fresh cultivated lavender immediately after 
collection. The mean of a large number of analyses oS the oils obtained gave the 
following results:— * 

. Density * Bolubility' Esters 

Lot. at 15^. in 70 per cent, alcohol, <%o. as linalyl acetate. 

a 0.894 5 vols, with difficulty 5045' 56.4 per cent. 

b 0.889 3 „ ' 7020' 50.8 „ 

c 0.887 3 „ ^ . 7050' 52.1 „ „ 

The three oils were submitted to distillation with a current of steam under reduced 
pressure, .giving the subjoined results: — 

(a) essential oi4-79, resinous residue 21 per cent. 

\^) ft n "*^» M » ^ w . »> 

• • 

The resinous ^ residues hat little odour, but gave the following percentages of 
ester: — (a) 65:4, (b) 62.3, (c) 62.6. 

The authors conclude from these results that the figures representing the total 
ester content are misleading and that it would be necessary to deduct the ester content 
of the inodorous resinous residues, when the real percentages of ester 'would be : — 
(a) 42.7, (b) 45.8, (c) 49.6/). 

It further results from the experiments that lavender which has been piled up to 
await distillation always gives a false titration, as resins with high ester content are 
formed by oxidation at the expense of the essential oil. According to Lautier Fils, 
the essential oils drawn from such flowers possess neither body nor fineness, although 
they are pure and have high titration figures for esters. They say that the value of 
lavender oil depends upon its "body" and upon its "bouquet**, which had nothing to 
do with the percentage of esters, and that oils from the Alps- with only 26 per cent, 
of esters were often far more valuable on account of their "bouquet", than other 
products with 45 per cent.*). 

The authors come to the following conclusions, which do not contain anything 
new;— Bouquet and body are two distinct factors. The body is approximately in- 
dicated by the ester titration. Absence of artificial esters must be ensured, in order 
that the titration figures should be genuinely indicative of value and purity. — There 
is no clear answer, however, to the question put in the beginning. 

We would say that these investigations do not alter the fact that, generally speak- 
ing, the value of lavender oils depends upon the percentage of esters. The more 
careful and appropriate the distillation of the lavender oil, the higher the percentage 
of esters and the less damage is done to the bouquet. 

The paper from the Roure-Bertrand Fils Laboratories^) contains extensive, though not 
altogether new details regarding the distillation, composition, analysis and adulteration 
of lavender oils. The best lavender oils are obtained, if due attention is given to the 
following points: — !) When distilling by direct heat, the flowers ought not to be 
soaked in water beforehand. The still must not be filled with too much water, as an 
excess of water diminishes the yield of oil and impairs its quality. 2) The distillation 



^) The authors seem to have overlooked that a second steam distillation must needs cause a further 
saponification of esters and an alteration of the oil. It is not stated whether the distillation was carried out 
under ordinary pressure or in vacuo. — ') This has been pointed out already by Birckenstock. Comp. Gilde- 
meister and Hoffmann, The Volatile Oils, 2"" edition, vol. Ill, p. 428. — ») Perfum. Record 12 (1921), 344. 



Report of Schimmel S Co. 1922. 






V^V • ; 



^.*' 



■;a. 



[i.f^ 



L''ii - \^ 



/*s;! 



.■<\- 



%^ 



t\ » 



should be carried through as quickly as possible (within an hour). 3) In consequence 
special stills with wide neck and wide steam-pipes must be used. 4) The oil passing 
over has to be cooled well, as cold water dissolves less oil than warm water. 

In order to obtain a uniform good product, growers ought to combine and distil 
the oil in joint distilling plants. 

A repoi^t has been published on the meeting of the Lavender Commission, held 
on May 17*^^ 1921, in the French Ministry of Commerce, containing the suggestions 
and propositions made by lavender growers, merchants and industrials. The Commission, 
however, has not arrived at a definite solution of all the questions concerning lavender^). 



a 



Lautier Fils^) examined a lavender oil of the following constants: — diso 0.894; 
p — 4^35'; soluble in 3 vols, of 70 per cent, alcohol; ester v. "48.8. In their opinion 
it had been adulterated with lauric ester, obtained apparently from the residues of 
cocoa butter manufacture, and small quantities of terpenyl acetate. 

I 

According to Humbert®), the sub-species of Lavandvla fragrans and L. delphinensis, 
created by )ordan, cannot be considered as distinct species, but merely as two extreme 
forms of variation in accord with the local conditions of habitat. Whereas the xero- 
philous Lavandula fragrans predominates in the sunny South of France and on the dry 
crests of the low mountains, the more moisture-loving L. delphinense thrives in the 
Morth, or in the higher valleys and higher mountains, where mists and rain are less 
rare, or again in the shadow of forests. Thus the Luberon shows on its arid brows 
(calcareous, of the lower Cretacean system), towards 1000 m. high, the most xerophil 
forms. But on descending from the summit towards the north, one meets on the 
slopes, less exposed to the sun and principally towards the base, where the soil is 
no longer puroly calcareous, but a soft Miocene formation and more hygroscopic, 
the whole gamut of transitions to forms presenting the maximum lengthening of axes 
and enlargement of the leaves. The transformation of one form to the other can be 
proved experimentaUy by planting the seed of the xerophil type in a damper soil or 
climate than the original station, or vice versa with the other type. The plant called 
L. Faucheana^) by Briquet and Rouy is also only a form of variation. 

It is otherwise with L. pyrenaka^ DC, which plant, found in the eastern Pyrenees, 
is distinguished by the much greater size of its principal bracts, which are as broad 
as long and almost conceal the calyx. The flowers are a little larger and the in- 
florescence appears bigger than that of Lavandula officinalis. The vast colonies of 
L. Pyrenaica begin where spike ceases and almost reach the summit of the mountains. 

Very seldom, in altitudes of from 800 to 1500 m., the white variety of lavender 
occurs. It was found on the Mount Ang^le near Myons, in the neighbourhood of 
Saturnin-les-Apt, on the Ventoux and near Ribiers. The corolla was white in each 
case, the calyx either blue, red or white. In order to obtain the essential oil of this 
highly fragrant species, A. Chiris*) tried to cultivate the plant from seeds. But only 
a few seedlings had white flowers, those of the others being mostly very pale. The oil 
obtained from the latter surpassed the ordinary lavender oil in ester content and aroma ^). 

It results from Humbert's explantions that the bracts and bracteoles are of special 
importance for the recognition of the different species and varieties of lavender. 
). Gattef osse '), in an article on French lavender and its hybrids, publishes six pictures 



ParfUm. modeme 14 (1921), 153. — «) Perfiim. Record 12 (1921), 343. — •) Per/Um. Record 12 (1921), 
252. — *) This type is not mentioned in the Index Kewensis up to 1910. — ») Per/um. Record 12 (1921), 405. 
•) There are no further details. — ') Parfum. modeme 14 (1921), 207. 



Commercial and scientific notes on essential oils. 45 

of such bracts and bracteoles of Lavandula officinalis, Chalx, L. latifolia, Vill. and • 
L, pyrenaica, DC. and their hybrids, taken from the ^'Office national des Matieres premieres 
ve'g^taW\ According to Humbert, the hybrids of lavender and spilte are more widely 
distributed than it was hitherto believed. Very frequent is the hybrid "Lavandula lati- 
folia < officinalis", in which the properties of L. officinalis preponderate, so that the 
gatherers do not know how to distinguish it from the true kind. The other hybrid, 
L. latifolia > officinalis, so-called "lavandin", resembling more L, latifolia, is better 
known to the distillers and avoided by them. Perhaps the lavender-fields in England 
and in Pornichet (Loire-Inferieure), which both yield oils of a low ester percentage, 
are cultivations of the hybrid ''/>. latifolia < officinalis'', 

Humbert states further that Lavandula Burnati, Briq.^ of the Maritime Alps and 
L. hortensis, Hy.*) resemble the "lavandin^*, whereas L. SpicaAatifolia, Albert, of the 
Var and L. Burnati van Fouresii, Coste, of the Causses de TAveyron, are more similar 
to "^. latifolia < officinalis". 

As regards two hybrids of Lavandula latifolia, Vill. and L. officinalis, Chaix, see 
page 118 of this Report. 

Oil of Lavandula Stoechas. — As results from the investigations of Roure- 
Bertrand Fils^), the oil of Lavandula Stoechas, L.'), described by us some years ago 
and which we afterwards designated as originating from L. dentata, L.^), came in reality 
from L. Stdechas after all. The confusion was due to the fact that we had originally 
received (1905) from Spain the flowers of the real L. Stoechas, whereas the second time 
(1915), when we asked again for the same kind, in order to have the plant determined 
by a botanical authority, the flowers of L. dentata were sent us by mistake. The sender 
maintained, however, that in either case the flowers had been taken from the same 
plant. — Roure-Bertrand Fils state that the oils obtained by them in different years* 
(1906) and 1921) from French Lavandula Stoechas differed verry little from one another 
and from the oil distilled by us (in 1905 from Spanish material), the constants being: — 
di6o 0.945 to 0.948, a + 47o to +49^56', acid v. 0.69 to 0.93, sap. v. 8.40 to 18.67, 
•ester v. 7.71 to 17.74, ester v. after acetylation 47.14, soluble in 5 vols, and more of 
60 percent, alcohol. The principal constituents of the oil are <i-camphor (semicar- 
bazone, m. p. 238°), <f-fenchone (oxime, m. p. 165°). Besides, fenchyl alcohol and per- 
haps terpineol and a phenol seem to be present. 

^ In order to obtain pure fenchone, the authors oxidized the oil with nitric acid and 
heated the product of the reaction repeatedly with 10 per cent, aluminium chloride. 
The resulting fenchone had the following constants; m. p. +3 to 5°, d2oo 0.9443, 
«Dao + 54°34', nDJio 1,4625, m^p. of the semicarbazone 174 to 176°. 

Roure-Bertrand Fils publish simultaneously an illustrated extensive botanical study 
by A. Camus regarding Lavandula Stoechas is, like rosemary, according to its whole 
structure a xerophilous plant which can stand a good deal of drought. It thrives on arid 
slopes, exposed to the sun, on heaths and steppes, frequently together with Cistus 
and Calycotome species, along the coast of the Mediterranean from Gibraltar to Asia 
Minor, on the Canaries, in Madeira, Portugal, Spain, Menorca, Sardinia, France, Corsica, 
Italy, the Balkans, Crete, Syria, Palestine, Morocco, Algeria and Tunis. Lavandula 
dentata, however, does not occur in France, but only in the coastal regions of part of the 
Mediterranean countries, such as Spain, Morocco, Algeria and perhaps southern Italy. 



*) Bull. BourerBertrand FiUj Oct. 1921, 3. — «) Comp. Beporta October 1905, 10; April 1908, 62. — 
*) BepoH April 1916, 28. 



^?^ 



S/ 46 Report of SchimmelSCo. 1922. 






'A 
"■■/■> 



/ 



Lemongras Oil. — Two samples of this oil was forwarded to the Imperial Institute 
p"'' from Seychelles. One of these samples was stated to have been obtained from Andro- 

^ f; '] pogon Schoenanthus, L. == Cymhopogon dtratus, Stapf, which has been grown in Seychelles 
!?*> for a long period. The oil had the following constants:— d^ 0.883, 'aD»o —0° 12', 

i<^v nptoo 1.486, insoluble in 70 percent, alcohol, practically soluble in 0.9 vol. 80 per cent. 

^Y ' alcohol at 15°, becoming turbid on dilution; citral, determined by the bisulphite method, 

1^ V 78.5 per cent. The oil is therefore of similar character to the West Indian lemongrass oil. 

%/;; The sample was valued in London at about 6 d. per oz., when commercial lemongrass 

!fc^ ■ oil. was quoted at 8 d. per oz. (February 1919). 

The second sample was stated to have been derived from a variety of lemongrass 
(Cymhopogon fleocuostts?) intrpduced into the colony from Cochin in 1911. The golden- 
yellow oil showed an ociour resembling that of lemongrass and also th^t of citronella oil. 
The constants were:— d^ 0.898, "dwo— 10°12', nozoo 1.484, insoluble in 70 percent. 
I alcohol, soluble in 1 vol. 80 percent, alcohol at 15°, be coming slightly turbid with 

^ 3 vols.; citral, 38 percent, (bisulphite method); geraniol, 20.5 percent. These data 

show that the oil differs markedly in composition from the East Indian oil and suggest 
that this "lemongrass" oil is not derived from Cymhopogon flexuosus, but from some 
other species. Possibly it may ever be a mixture of lemongrass and citronella oils. 
We gather from and English periodical') the following statements concerning the 
so-called West Indian lemongrass oil derived from Cymbopogfin citrutv^y Stapf which is 
known to differ from the East Indian oil by its low solubility in alcohol. The oil was 
originally distilled in Travancore and came to England via Cochin for the first time 
in 1832. When later the industry extended northwards to Malabar, Calicut became the 
centre of distribution. Recently, the oil is being distilled in Assam and )ava. Before 
the war, from 2OO0 to 3000 cases, each containing one dozen quart bottles of oil (each 
.1.236 litres) were exported annually from Cochin to Bombay as well as to Mew York, 
Hamburg, and London. 

Oil of Leptospermufn flavescens. — In the oil of Ijeptospermum flavescens var. 
citratum, Challinor, Cheel and Penfold*), some years ago, proved the presence of a 
phenol yielding a benzoate of Ihe m. p. 67°. This phenol, termed leptospermol, has now 
been investigated closely by Penfold'). The amount of the phenol in the oil varied 
according to the different localities from which the material was collected, and ranged 
between 0.75 and 8.0 per cent. The leptospermol (C14H20O4.?) was abstracted from the 
oil by shaking with a 3 percent, caustic soda solution and was a somewhat viscous 
liquid, almost colourless, with a pleasant and characteristic odour, and the following 
constants:— b. p. 145 to 146° (10mm.), 275 to 278° (770mm., uncorr.), dwo 1.073, 
« + 0, noMo 1.5000. In alcoholic solution, it gave with ferric chloride a brilliant distinctive 
orange-red coloration; with copper salts, an intease blue coloration. Derivatives of 
the phenol were not obtained. The phenol bears a very strong resemblance to the 
phenol tasmanpl*) found in various eucalyptus oils, but differed therefrom by the 
refractive index and the boiling-point under reduced pressure. 

Oil of Leptospermum grandif lorum. — From the leaves of Ijeptospermum grandi- 
fioruMy Lodd., a myrtacea growing in the river-beds in New South Wales, A. R. Penfold*) 
obtained 0.61 per cent, of a rather viscous, dark brown oil. After shaking with dilute 



1) Perfum. Record 12 (1921), 50. — «) Comp. Report 1919, 34. — •) PerfUm. Record 12 (1921), 336. 
— *) Comp. Report 1916, 3 J. — ») Joum. Proceed. ofR. S. ofN. S. W. 54 (1921), 197. Ace. to Bull. Roure-Bertrand 
FiU, October 1921, 159. 



Commercial and scientific notes on essential oils. - 47 

sodium hydroxide solution the oil exhibited the following constants: — d^o 0.9324, 
«D — 2<^42', njjjoo 1.5048, ester v. 7.2, ester v. after acet. 40.98; insol. in 10 vois. of 
80 per cent alcohol. By repeated fractionation of the oil in presence of sodium, under 
10 mm. pressure, the auther obtained the fractions: — 123 to 125° (diso 0.910, Op — 6.2°, 
nDsoo 1.4967) and 129 to 132 o (d^o 0.921, a^ + 0.72 o, aDMo 1.5063). These two fractions, 
which agreed in their constants fairly with aromadendrene and eudesmene^), gave 
likewise the colour reaction of these sesquiterpenes with bromine and with sulphuric 
acid'). In addition, the oil contained, besides a small amount of phenolic bodies, a 
sesquiterpenic alcohol, which the author was unable to describe more closely. 

4 

Oil of Leptospermum odoratum. ^- On distilling the leaves and twigs of Lep- 
fqspermum odoratum. Cheel, a plant likewise occuring in the valleys of Mew South Wales, 
A. R. Penfold^) obtained on the average 0.75 percent, of a yellow oil with an odour 
reminding of terpenes and roses. Its constants differed according to the time of 
collecting (August, 1917, May and October, 1920) and ranged as follows:— dis© 0.9163 
to 0.9280, ttD ~ 16,32 to —33.02°, ni>Mo 1.4960 to 1.4990, ester v. 5.6 to 7.2, ester v. after 
acet. 57.00 to 91.93, sol. in 10 vols, of 80 percent, alcohol, in orie case insoluble in 
80 per cent, alcohol. In addition to combined acetic acid, the oil contained above all 
butyric acid in combined state. In the fraction b. p. 60 to 90° (10 mm.), «- and ^-pinene 
were proved to be present by means of characteristic derivatives*). The fraction 125 to 
140° (10 mm.), one-half of the oil, contained nearly equal parts of eudesmene and 
aromadendrene which were identified by means of their constants and their colour 
reactions"). This natural eudesmene differed from the synthetical dextrorotatory pre- 
paration*) by its optical rotation of —53°. Fronf the solid distillation-residue (10 to 
15 percent of the oil), there Was obtained, by crystallisation from dilute alcohol, 
eudesmol, m. p. 79 to 80°, b. p. 156° (10 mm.), [alojoo + 31.80°. Furthermore, the oil 
appeared to contain about 2 per cent of an alcohol not further dealt with, which gave 
rise to the rose-like odour of the oil. 

Oil of Lindera sericea. — A. Spann'') reports that according to official )apanese " 
statistics an essential oil is distilled from the lauracjsa Lindera sericea, Blume (Kuro- 
moji®)). The producing districts, Hiogo ken, Shimane Jcen and Hiroshima ken, are in 
the southern part of the main island Honshiu. In 1915, 9438 kin of oil were obtained, 
representing a value of 9880 yen. 

Machilus Oil.— Seisi Takagi^) obtained from the wood shavings of the Formosan 
Lauracea Machilus Kusanoi, Hayata^^), on distillation, a pale yellow, viscous oil with 
the constants: — d^ 0.9815, Moro + 18.20°, acid v. 0, sap. v. 0, sap. v. after acet 50.21. 
On fractionation under 5 mm. pressure, 120 g. of the oil gave 6 g. oil b. p. 125 to 140° 
42 g. b. p. 140 tp 149° 25 g. b. p. 149 to 159°, 9 g. b. p. 156 to 170° — these three 



*) Cf. Reports April 1902, 31; October 1918, 59. — ■) In the literature, colour reactions are only given 
for aromadendrene (cf . Baker and Smith, A Research on the Eucalypts, 2"'' ed. p. 417 ; Gildemeister and Hoffmann, 
The Volatile Oils, 2"<* ed. vol. Ill, p. 275) but not for eudesmene. — «) Joum. & Proceed. ofR. S. ofN. S. W. 54 
(1921), 197. Ace. to Bull. Roure-Bertrand Fils, October 1921, 159. — *) Details in this respect are missing in the 
abstract. — *) Cf. the footnote above, with Lept. grandifl. — •) Cf. Report October 1913, 59. — ') Der 
Tropenj^mer 24 (1921), 167. — ') Details concerning the Kuromoji oils obtained from the leaves and other 
parts of the plant are to be found in Gildemeister and Hoffmann, The Volatile Oils, 2p^ ed., vol. II, p. 502. 
— •) Joum. pharm. Soc. Japan 1921, H° 473 (2n<* communication). From a copy kindly forwarded to us. 
Unfortunately, we hitherto did not come across either the first communication or an abstract thereof. — ^^) Is 
not mentioned in the Index Kewensis of 1910.- 




48 Report of Schimmel S Co. 1922. 

fractions solidify to a crystalline mass — , and 10 g. of a viscous oil, b. p. 170 to 185^. 
Repeated crystallisation of the solid fractions yielded a body CisHmO, machUol; 
m. p. 79 to 80°, b. p. 160° (14 mm.), Md^o + 42.87°. On treatment with acetic anhydride 
and sodium acetate the body is acetylated but partly; neither is formed a phenylurethane 
with phenylisocyonate nor a benzoate according to Schotten-Baumann. Reduction with 
platinum black and hydrogen yielded dihydromachilol CisHgsO, m. p. 82 to 83°, b. p. 157 
to 158 (14 mm.), [«]dmo + 16.43°. By oxidation with potassium permanganate, m^chilol 
passed over into dihydroxymachilol, or machilene glycerol Ci6Hi80(OHj+HtO, m.p. 1 10°, 
Mdmo — 25.91°; monobenzoate, m. p. 142°. This body proved to be identical with 
a-dihydroxyatractylol which the auther obtained, in addition to /^-dihydroxyatractylol 
<m. p. about 78°, [aJouo + 24.68°), on oxidising atractylol by the same reagent. Hence, 
machilol is a bicyclic, tertiary sesquiterpene alcohol. 

When machilol was heated with formic acid, machilene C15H24 resulted; b. p. 120° 
<3 mm.), d^o 0.9109, Mdbo + 58.73°, n^tso 1.51257; Liebermann's reaction: first blue, then 
green, and after some standing dark blue. On reducing machilene with hydrogen and 
platinum in glacial acetic acid, tetrahydromachilene CisHm was formed; b. p. 132° 
<11 mm.), d\^ 0.8964, Wdioo + 37.04°, npioo 1.48645. 

Machilene is no uniform body, but a mixture of probably two isomerides, for on 
abstracting water from machilol by weaker-acting reagents, an isomeride of machilene 
is formed with higher rotatory power («d about + 100°). 

On reducing atractylene (b. p. 108 to 109° [3 mm.], d^ 0.9189, [«]di30 + 78.35°, 
tioiso 1.51795) catalytically, tetrahydroatractylene is formed (b. p. 129 to 130° [10 mm.], 
d^ 0.9030, [«]di8o + 36.99°, nouo 1.49589), a liquid with a feeble but pleasant odour. 

Since the tetrahydro derivatives of machilol and atractylol agree very closely in 
their qualities, Takagi ascribes to atractylol (or atractylene) and to machilol (or machilene) 
the same carbon nucleus, both bodies differing merely by the position of the double 
linking and the hydroxyl group. 

Massoi Bark OH. — According to the Imperial Institute^), the Massoi bark from the 
Fiji Islands and Mew Guinea and sold on the Singapore market, comes from Cinnamomum 
pedatinervium, Meissn. (identical with Massoia aromatica, Beccari [?])*). 

; Milfoil Oil. — An extensive publication on this oil has been published by 
R. E. Kremers^). The crude material, Achillea Millefolium, L. serving for the investigation 
was collected from the middle of June to the middle of July, freed carefully from foreign 
matter, and dried immediately at the open air. About 1200 pounds of fresh herb weighed 
after three days' drying 420V« pounds or 190.7 kilos, and yielded 892 g. of oil, or 
0.467 per cent, of the dry herb. This exceptionally high*) yield of essential oil was 
arrived at by cohobating the distillation-water, thus obtaining in addition to the principal 
oil, 21 per cent, of "water oil", calculated on the former oil. 

Firstly, the "water oil" was subjected to fractional distillation. The fractions, 
b. p. between 64 and 90°, proved to contain formaldehyde (by its odour, and Schiff*s 
reagent), methyl alcohol (methyl salicylate, formaldehyde, and 3, 5-dinitrobenzoic methyl 
ester), ethyl alcohol (iodoform reaction), acetone (reaction with sodium nitroprusside 
and iodine potassium iodide), furfural (aniline acetate), borneol (m. p. 203 to 204°). 




^) Bull. Imp. Inst. 19 (1921), 338. — *) As to the still doubtful origin of the Massoi bark of commerce 
see Gildemeister and Hoffmann, T^e Volatile Oils, 2"<* edition, vol. II, p. 498. — •) Joum. Americ. pharm. Assoc. 
10 (1921), 352. — *) From dried blossoms once even 0.485 per cent, oil were obtained, from fresh blossoms, 
as a rule, 0.07 to 0.25 per cent. Cf. Gildemeister and Hoffmann, The Volatile Oils, 2^^ ed., vol. Ill, p. 617. 



Commercial and scientiffc notes on essential oils. 



49 



The constants of the principal and the Aqueous oil (together with those observed 
by Miller*) in 1916) were as follows: — 





Principal oil 




Aqueous oil 




1916 . 1919 


1916 


1919 


dl70 . ... . . . 


0.915 0.913 


d26o 0.939 0.948 and 0.959 


Acid value . , . 


7.24 4.27 2) 


37.0 


— 


Ester valuci . . . 


2.2 5.65«) 


7.6 


17.7 


§apon. value . . 


9.44 , 10.92=) 


44.6 


— 


Ester V. after acet. 


23.5 ' 17.8 


51.8 


50.9 



These figures show that the water oils contain more free acid, more esters and 
more free alcohols than the principal oils. The following constituents of the cohobated 
oil were identified: — A valeric acid (in all probability; silver salt), a large quantity of 
impure borneol, furfural (aniline acetate reaction), and traces of eugenol (benzoate, 
m. p. 69 to 70°). 

The main oil was separated by fractionation, first under atmospheric pressure, into 
10 fractions boiling between 85 and 174*^, then under 30 ram. pressure, into 10 more 
fractions boiling between 75 and 125 <^. Miller') had proved formerly the presence in 
these fractions of following bodies: — valeric, salicylic and butyric acids, aldehydes, 
pinene, limonene, camphor, borneol, and cineole. In addition to these constituents 
which, except limonene, were also identified by Kremers, the latter author succeeded 
in identifying nopinene (nopinic acid, m. p. 126^; nopinone semicarbazone, m. p. 188°). 
The constants of a saponified fraction of the b. p. 90 to 95° pointed to the presence 
of thujone (djso 0.929, «— 3.0° nD»o 1.4588). The tribromide (Wallach) showed the 
m. p. 121°; the semicarbazone was readily formed, but was either a mixture of the 
derivatives of «- and /^-thujone, or of thujone with that of another ketone. 

From 100 g. of a fraction boiling above 140°, Kremers obtained 35.5 g. of a blue 
oil, containing azulene, b. p. 135 to 136° (1.1 mm.), and 59 g. non-blue oil. With alcoholic 
picric acid solution, azulene yielded instantly the picric acid addition compound. After 
removal of the azulene by means of phosphoric acid, the oil was fractionated (pressure, 
5 to 0.1 mm.) into 8 fractions boiling between 80 and 180°. From the portions boiling 
between 100 and 115° (0.5 mm.) the author obtained, by distillation with sodium, a 
fraction with the constants: — b. p. 105 to 110°, dwo 0.916, « -—13.75° (100 mm. tube), 
n 1.4990, mol. refr. 65.4, which yielded a benzylamine base, m. p. 172 to 173°, and a 
hydrate, m. p. 94 to 95°. The presence of caryophyllene, therefore, must be considered 
as proved. 

As a supplement to Kremers* notes on the work of Miller on milfoil oil, we add 
the following statements culled from Miller*s paper, the copy of which reached us or^y 
recently. E. R. Miller') obtained by stean>distillation partly from the entire (fresh or 
dried) plant, partly from the flowers or the leaves of Achillea millefolium^ L. cultivated 
near Madison a series of oils, all of which were dark blue. The flowers yielded more 
blue oil than the leaves. Distillation of the lower two-thirds of the plant is unprofitable. 
Drying of the plant apparently produces no change in either the quantity or quality of 
the oil. Apparently, there exist some definite relations between yield on one hand and 
density and refractive index on the other. As stated above, Miller separated the oil 
into various fractions and proved the existance of following constituents in the oil:— - 
I' and d'p'mene (nitrosochloride, m.p. 102 to 103°; nitrolpiperidin, m.p. 119°), Z-limonene (?) 



*) Cf. Bull. 785, University of Wisconsin. Sec also further below on this page. — *) These figures do not agree 
with each other. — ') Bull. Univ. Wisconsin No. 785. 

4 



50 Report op Schimmel S Co. 1922. 

(odour and density of corresponding tractions, no nitrosochloride being obtained), /-borneol 
(m. p. 202 to 203°; acetate, m. p. 29°; phenylurethane, m. p. 139°), bomyl acetate and 
other bomeol esters, tcamphor (oxime, m. p. 119°; aemicarbazone, m. p. 235 to 236°), 
cineole (resorcinol compound; iodole derivative, m, p. 106 to 107° instead of 111 to 112°), 
salicylic acid (colour reaction with ferric chloride), aldehydes (presumably two, SchifTs 
reagent), formic, acetic, butyric (?), and isovaleric acids (silver salts), a non-volatile add 
or a lactone, and a blue constituent of high b. p. (145° at 15 mm.), 

Monarda Oils. — A series of methoxyl estimations in monarda oils undertaken 
partly with unchanged oils, partly after removal of the phenols in the hope that this 
constant would prove characteristic, has been published by D. C. L. Sherk'). In the oils 
of Monarda punctata, the content of methoxyl amounted to 0,11 to 0.36 per cent. The 
non-phenolic parts of the oils differed in their methoxyl value hardly from the original 
oil. fience, on the separating ol the phenols a methoxylated body must have dissolved 
in the aqueous alkali. Such a body is the monomethyl ether of thymohydroquinone, 
since the dimethyl ether and thymol methyl ether, otherwise constituents of the oil, 
are non-phenOlic bodies, i. e., insoluble in alkali. Sherk was able to prove that the 
ailialine extract of an oil from Monarda fiatulosa contained a pale reddish oil with 
1.14 per cent, methoxyl and leaving on distillation a tarry residue with 0,95 to 1, 17 per cent 
methoxyl. The part of the oil extracted from the alkaline liquid by means of ether 
contained, in addition to carvacrol, thymohydroquinone. 

From an oil of Monarda punctata, the thymol of which had been removed for 
the greater part by freezing, Sherk obtained ciystals of thymohydroquinone and a 
black, tarry residue with 0.61 to 1.48 per cent methoxyl. This residue consisted for 
one-third of thymohydroquinone, m. p. 141°, which was isolated therefrom by fractional 
distillation. 

It is well-known that the essential oils obtained by redistil I ating the dlstiliation- 
water of essential oils show properties differing from those of the principal oil. In the 
most cases, especially the specific gravity of the latter oil is lower than with the 
"water oil", as the water-soluble constituents of essential oils show, as a rule, a higher 
density than the bodies insoluble in water. As we gather from a paper by E. R. Miller') 
on "Redistillation of aqueous distillates resulting from the production of volatile oils", 
the specific gravity of the principal oil from Monarda flstwlma. L amounted to 0.9280, with 
the "water oii" ol the same plant, to 0.9700. Wormwood oil, however, behaved accordi'-j^ 
to Miller, differently, since the "water oii" was lighter owing to the content of thujontl. 
The yield of wormwood "water oil" ranged between 6 and (?) 37 per cent, of 'the aqueous "■ 
distillate, according to the maturity of the plants under investigation, ' 

Oil of Mosla grosserata.-^Y, Murayama') discovered in the oil of Moda grosserata, 
Maxim., a new terpene, moslene (comp. p. 50 of this Seport). 

Oil of Mosla Hadal.— As we hear from Asahina, the oil*) investigated some years 
aeo bv Y. Muravama did not come from Moda .iajwnka. Maxim., but from Mosla Hadai 



Commercial and scientific notes on essential oils. 



51 



Oil of Mosla japonlca. -— Since Hada's discovery of thymol in the oil of Mosla 
japonica, Maxim, this plant has been cultivated in Japan with the object of obtaining 
this phenol. On investigating the terpene fractions of the oiP), Y. Murayama*) found 
a new terpene named by him moslene. This body was found in a fraction with the 
b. p. 59 to 60° (to mm.) or 173 to 175° (ord. pressure) obtained from an oil after the 
thymol had been removed with alkali. The fraction, which was not quite free from 
oxygen, showed some resemblance with the terpene crithmene obtained by Francesconi 
and Sernagiotto**) from Italian samphire oil, and had the following constants: — diso 0.8528, 
no 1.48228; nitrosochloride m. p. 111°, nitrolpiperidide m. p. 142 to 143° nitrolanilide 
m.p. 126 to 128°, dihydrochloride m. p. 52°, nitrosate m. p. 114°. 

On treatment of the nitrosochloride, in alcoholic solution, with sodium, a body 
(CioHi8)2N20 resulted; yellow needles, m. p. 52 to, 53°; sometimes, a less soluble 
substance (CioHi8)2N2, orange -yellow 
leaflets, m. p. 85 to 87°, was formed, 
which proved to be identical with azo- 
p-cymene (m. p. 87°); formation of the 
latter by reduction of ^-nitrocymene. 
The identity of the yellow body (m. p. 52 
to 53°), too, with azoxy-i?-cymen6, is, in 
Murayama's opinion, established, in 
so far as the yellow body and azoxy- 
^cymene, on reduction, both give rise 
to the identical benzidine derivatives 
([CioHis • NHa • HC1]2, decompos. p. 292°;. 

According to Murayama, moslene, therefore, is a dihydrocymene, with two double 
bonds located most probably in the benzene nucleus. Since amongst the five isomerides 
complying to these conditions three are known, i. e., «-terpinene, /-terpinene, and a-phel- 
landrene, moslene appears to be constituted as stated in one of the above formulas. 



CHs 
I 
CH 



CHg 

I 
CH 



HoC 







C 
I 
C8H7 

I. 1 : 2-Dihydrocymene. 



CH 

C3H7 

II. 1 : 4-Dihydrocyniene. 



Miistardseed Oil. — Up to now it was only known that the insoluble deposits, 
forming sometimes in mustardseed oil, consisted of an orange yellow compound, 
containing carbon, nitrogen, hydrogen and sulphur. H. Kunz-Krause*) investigated this 
compound more closely. He comes to the conclusion that it is not a uniform body, 
but is composed of allylamine sulphate, soluble in water, and jps^t^c^o-sulphocyanogen, 
insoluble in water. In addition to these two chief compounds, there are present most 
likely small quantities of xanthogenic acid derivatives, tso-sulphocyanic acid and allyl- 
substituted urea. As the constituent of the deposit which could be washed out with 
water, smelled distinctly of mustardseed , oil, after having been stored over caustic 
lime for several months, the author thinks that the insoluble part decomposes and 
splits off allyl mustard oil. It is probable that a solid polymeride of wo-sulphoallyl 
cyanide (S = C=;=N — C8H6)n forms, perhaps in combination with j?set*(io-sulphocyanogen, 
CsHSsMs» formerly called per-sulpho-cyanogen*). The author gives as the reason for 
the formation of the deposit and of the other accessory compounds always present in 
mustardseed oil, the decomposition of three molecules of mustardseed oil in sulphur 
and allyl cyanide, and certain intramolecular changes of the mustardseed oil, due to 



1) Cf. Bericht (German) 1920, 42. — ^ Joum. pharm. Soc. Japan 1921, No. 475. According to a reprint 
kindly forwarded to us. — ') Cf. BepoH October 1918, 94. — *) Arch, der PAarm. 269 (1921), 16. As per a 
reprint kindly sent u^. — *) I. Maier, Die atherischen Ole, Stuttgart 1862, p. 167. 

4* 



52 Report OF SCHiMMEL § Co. 1922. 

the influence of air, light and moisture. In consequence, mustardseed oil ought to be 
kept always in small, absolutely dry vessels and guarded against air and light. 

According to A. Cauda ^), the percentage of mustardseed oil is smaller in southern 
districts (Sicily), than in the more northern regions (Piemonte, Forli), the content of 
oil being the smaller, the greater the content of fatty oil. During germination, the 
content of mustardseed oil, which diminishes on etiolation, remains fairly constant. 
Black mustardseed contained 0.284 per cent, the green germs 0.280 per cent, the 
etiolated germs 0.170 per cent of essential oil, calculated with reference to air-dried 
substance. The test was carried out by oxidizing mustardseed oil with bromine water 
and depositing the sulphuric acid formed as baryum sulphate. 

V. Massera*) states that the Italian Pharmacopoeia, 3''^ edition, contains erroneous 
indications for the determination of mustardseed oil. Instead of 9.5 to 10 cc. of 
ammonium sulpho-cyanide solution, 15 to 15.5 cc. are required*). ' 

Neroli Oil.— See Orange Blossom Oil, p. 53 of this Report 

Oil of Oclmutn gratlssimutn. — An oil of this plant originating from Mahe 
(Seychelles) and differing entirely in character from the oil produced in the Ivory 
Coast and Central Africa, has been mentioned by us in our Report 191?, p. 36, where 
^e quoted the constants. In the meantime, the plant has been identified at Kew as 
Ocimum gratissimum, L.^ and a sample of the oil (d 11^0.996; "d — 12.7°; nD»o 1.532; 
phenols, 55 per cent) was investigated by O. D. Roberts*). 

After removing the free acids (0.2 per cent, probably acetic acid) and the free 
phenols (entirely eugenol, b. p. 252 to 253°; benzoyleugenol, m. p. 69 to 70°), an oil 
remained resembling in odour the oil of sweet basil, with the constants: — d|| 0.901 3; 
ttp — 15.0°, nDJoo 1.513, ester v., 4.5; ester v. after acet 101.5. On distillation under 
20 mm. pressure the oil yielded the fractions:— 1. B. p. 70 to 85° (16 per cent of the 
original oil); 2. b. p. 85 to 100° (15 per cent); 3. b. p. 100—135° (9 per cent). Fraction 1 
consisted chiefly of ocimene (b. p. 70 to 75° [20 mm.]; d|f| 0.8029; inactive, npaoo 1.4855; 
dihydromyrcene, djf§ 0.7777; noi,© 1.4500; mol. refr. 47.7; tetrabromide, m. p.88°). Frac- 
tion 2 recalled the odour of linalool; on oxidation with chromic acid mixture a citral- 
like odour was produced. Fraction 3 had a distinct odour of methylchavicol, but 
judging from the specific gravity, no large proportion of this compound was present. 

The composition of the sample, therefore, is approximately as follows : — Terpenes 
(ocimene), 16 per cent.; phenols (eugenol), ,55 per cent; phenol ethers, calculated as 
methylchavicol, 5.6 per cent; alcqhols, probably linalool, 13 percent; esters, 0.6 per cent; 
residue and loss, 9.8 per cent The oil appears to be rather similar in composition to an 
oil of sweet basil of the variety Selasih MeJcah from Java, as examined by van Romburgh^). 

on of Ocimum vlride. — A sample of the oil from Ocimum viride, Willd. was 
forwarded to the Imperial Institute from Seychelles in 1919 and revealed on examination^) 
the following properties: — dj^ 0.910; ajj-f-0.75°; nDapo 1.497; phenols, consisting almost 
entirely of thymol, 37 per cent, whereas previous samples of the oil of identical origin. 



1) Staz. Sperim. Agrar. Ital. 62 (1919), 544. According to Chem. Zentralbl,19U, I. 814. — *) Boll. Chim. 
JVirm. 60 (1921), 62. As per the C/iem. Zew^raWi. 1921, IV. 391 . — •) Years ago, when discussing the Italian 
Pharmacopceia, we have already pointed out this mistake. Comp. Beport April 1910, 131. — *) Joum. Soc. 
chem.Ind. iO (1921), T. 164. — •) Comp. also Gilderacister and Hoffmann, The.VolatiU Oils, 2"" ed., vol. Ill, 
p. 578. — •) BuU. Imp. Inst. 18 (1921), 348. ^ 



Commercial and scientific notes on essential oils. 53 

investigated in 1917, contanied 52 to 62 percent.*). Equally, the yield of oil in the 
present instance was less (0.2 per cent.) as compared with the former yields (Q.5 and 
0.45 per cent.) obtained in 1916 and 1917. It was of importance to as certain whether 
this low yield of oil was due to faulty distillation or whether it was due to the stage 
of growth or condition of the leaves. Since the oil is of importance for the manu- 
facture of thymol, it was suggested that the conditions be determined for obtaining 
the largest yield of oil containing a maximum of thymol. . 

Olibahum Oil, — See Frankincense Oil, p. 36 of this Report. 

Orange Blossom OH. — According to news from the South of France, the probable 
result of the coming Jlower ctop will be aboiit one fourth of the normal average. As 
it is known, the trees had suffered from the severe frost in the winter 1919/20 to 
such an extent that part of them had to be cut down to the roots, whereas from 
others the largest branches had to be sawn off. These trees, of course, do not come 
into consideration at all for the next crop. Those^ however, which in warmer places 
were less exposed to the frost have plenty of buds and promise fair, unless there be 
frosts again before the beginning of May. Mothing can be said so far as to the price 
of the blossoms, but after having paid 10 francs per kilo in 1920 and Fr. 12.50 in 
1921, one hopes to see them this year reduced to about one-half. 

W. Miemz*) states that the production of neroly oils in Italy, especially in Sicily, 
which so far had been unable to compete with the French distillates, is improving 
also in quality. He says that it ^is scarcely possible to tell any difference between 
Italian and French oils. 

On account of our own experience we are a little more sceptical. What we have 
seen so far of Italian oils does not come up by far to the French qualities. This 
holds good even for the samples received quite recently. Apart from the odour, there 
is a difference in the constants. We have often had the impression that one is a 
little careless in the Selection of the material', distilling not only flowers, but leaves, 
branches and unripe fruits. It is also possible that the blossoms of the bitter and 
' the sweet orange-trees are used indiscriminately and that the state of development of 
the blossoms is not sufficiently taken into consideration. In France, only the fully 
developed blossoms of the bitter orange-tree, gathered with care, are distilled, and 
this accounts perhaps for the superiority of the French product. 

Origanum Oil. — In our Report of 1918, page 37, we quoted as a communication 
of the Imperial Institute^) the phrase; "Ordinary Cyprus oil is said to contain merely 
thymol" and added that this seemed to us rather doubtful. It has been found out 
meanwhile that the mistake was on our side, as the original English text states cor- 
rectly: "Cyprus origanum oil only contains carvacrol". 

Oil . of Orixa japonica. — By steam distillation of the leaves and twigs of 
Orixa japonica^ Thunb. (CelastriLS Orixa), a. celastracea known in Japan as Koktisagi, 
Y. Shinosaki*) obtained about 0.01 per cent, of a light brown oil having a characteristic 
odour recalling that of the oil of Lindera sericea, Blume"). The constants were: — 

Comp. Report 1918,36. — «) Deutsche Parf.-Ztg. 7 (1921), 161. — . ») Bull: Imp. Inst. 15 (1917), 306. — 
*) Jotirti. chem. Ind., Japan 24 (1921), 563. Joum. Soc. chem. Ind. 40 (1921), A. 560. — ») Hitherto, nothing is 
kjiown as to the essential oil of this lauracea. 



54 Report of Schimmel S Co. 1922. 

di50 0.8974; [a]D~4.50; nptoo 1.4750; soluble in 2 vols. 80 per cent, alcohol; acid v. 0; 
sap. V. 37.27; sap. v. after acet. 100.3. Its principal constituents are camphene, linalool, 
a terpene alcohol and its ester ^). 

\ Orris-root Oil.— The last crop of Flbrentine orris-root is estimated by competent 

people at from 250000 to 300000 kilos, a very unfavourable result. The high costs 
of labour do not induce anybody to having the roots dug up, the less so as there 

ff' are considerable stocks from last year, owing to the sluggish demand. As these ^old 

stocks are said to amount to about 300000 kilos, there would be 300000 to 350 000 (?) kilos 
available, altogether i. e, about the same quantity as has been obtained in an average 

I' crop of the last ten years. As there i$ very little business, the dealers try to make 

the consumers believe that there will be a rise, but it Seems rather doubtful whether 
they will succeed in the long run. 

Our two qualities of orris-root oil are in good demand, which, proves that they 
|: have maintained their leading position in perfumery, in spite of the manifold impedi- 

ments of the post-war times. 












^, 



.V* 



/ '■ 



Whereas in Italy, and especially in the province of Florence, Iris germanica, L. 
and Iris pallida, Lam., are cultivated above all, in France Iris jlorentina, L. = Iris alba 
is grown almost exclusively, though on a smaller scale. Some few iris plantations are 
said to be found in the departments of Var and Bouches-du-Rhdne, according to 
A. Roulet'). The largest plantation exists in the department of Ain, where the plant 
was cultivated already in 1835. It covers from 10 to 30 hectares, according to the 
year. PelHssier') says that the cultivation is restricted to the small communities of 
Anglefort and Corbonod, comprising a distance of 10 to 15 kilometres on the right 
bank of the Rhdne. The iris, which adapts itself to every calcareous soil, if not too 
fresh and too. moist, thrives best on good alluvial soil. In Ain the plant is cultivated 
on tilled, calcareous steppe-land. Very rich soil does not suit the iris, nor should 
stable manure be given, as it influences the aroma of the rhizomes unfavourably. 
Artificial nitrogenous fertilizers do not seem to have any effect on the development 
of the plant, whereas potash compounds favour the aroma and the growth of the 
rhizomes. Others recommend on the contrary 15000 to 20000 kilos of stable manure 
or 8 to lOOOO kilos of oil cake per hectare after the second or third rotation of crops. 

Planting takes place already towards the end of August, for which purpose the 
young shoots of two-year-old rhizomes are kept. They have no swelling yet, but roots, 
and are planted 25 to 30 cm. apart in every direction and 10 cm. deep. Sometimes 
they are first kept in a nursery and planted out in the following autumn. 

The best remedy against "iris rot"*), it is said, is to improve the soil, in case it 
should be too damp, and to disinfect it with carbon sulphide (200 grams per square metre). 

In the department of Ain, the rhizomes are collected already in the second year, 
from August to October; in Tuscany, in spring of the third year. The rhizomes are 
not, as in Italy, first soaked in water, but cleaned and freed from the black skin by 
women and children. Sometimes the rhizomes are cut in pieces, 5 to 10 cm. long 
and 3 cm. thick. After having been soaked in water for 24 hours, they are spread 
on bast mats and dried in the sun or in a moderately warm stove. The yield of a 
two year old plantation comes up to from 5 to 6(X)9 kilos of dry rhizomes on an 
average, corresponding to from 10 to 12000 kilos of fresh rhizomes. 



^) Details are not given in the abstract. — *) Par/um.modeme 18 (1920), 154. — *) Cf. BepoH October 1915,65. 



i 

r 
1 



;v. 



V Commercial AND scientific notes on essential oils. 55 

Paltnarosa Oil. — A sample of this oil, forwarded in 1917 from the United Pro- 
vinces of India, was investigated in the Imperial Institute^) with the following result: — 
d||0.889; aj)— 0.41^; nD»o 1.477; sol. in 1.8 vol. of 70 per cent, alcohol; acid v. 1.6j 
ester v. 11.8; total alcohols, calculated as geraniol, 90.7 per cent. The oil answered 
nearly fully the requirements of a good commercial quality, yet it smelled slightly of 
lemons and had not the clean geraniol odour of highest grade palmarosa oil; possibly, 
the sample contained lemongrass oil. 

A. second sample of palmarosa oil distilled at Cawnpore contained a lower per- 
centage of total alcohols and its aroma was not quite equal to that of the previous 
sample. Its c6nstants were:— 41^0.889; aDjoo+ 0.32 O; nDJoo 1.472; sol. in 1.9 vol. 
70 per cent, alcohol; acid v. 0.8; ester v. 28.0; total alcohols, calculated as geraniol, 
85.5 per cent. 

• - ■ , 

Patchouly Oil. — Whereas the true patchouly plant of commerce, Fogostemon 
Patchouli, Pell., or P. Cahlin, Benth., is cultivated only to a very small extent in Java, 
there are extensive patchouly fields in the Morth of Sumatra, especially near Tapa Tiian 
in the Atjeh district*). In the beginning the natives cultivated the plant, nilam, in 
order to prepare with the aid of its leaves a hair oil for their, own use, and'the export 
of the dried leaves did not begin earlier than about ten years ago. The plantations 
extended in* the same proportion as the prices rose (at present 15 florins per picul, 
as compared with only 3 florins .ten years back). Now they are. not only resti*icted 
any more to" Tapa Tuan, but are also found in the districts of Sama Dua, South-Dho, 
Phoa and Menke. 

Before the war, France and Germany were the chief European importers of 
patchouly leaves. In 1913, France imported 3659 piculs and Germany 4975 picul$ from 
Penang; in 1914, France imported 93 piculs from Singapore and 1655 piculs from 
Penang, whereas Germany took 2973 piculs from PenangT In addition, considerable 
quantities went to British India, Hongkong and, since 191 1> to the. United States. 
Japan and Canada were buyers for the first time in 1918, the former importing 259 piculs 
and the latter 481 piculs from Singapore. ' 

According to a report of the Dutch Chamber of Commerce in New York') the 
distillation of the oil has been started in Atjeh, the export centre of patchouly leaves. 

Roure-Bertrand Fils*) examined two patchouly oils from the neighbourhood of 
Kotta-Radja (Sumatra), obtained by distillation of leaves and stems, and found the 
following constants: — 

leaf oil stem oil 

di5o 0.9698 0.9739 

a\ . . — 5204' —5408' 

acid V 1.2 8.7 

ester v 6.7 1.3 

„ „ after acetylation . . . 26.13^) — 

solubility in 85 per cent, alcohol turbid turbid 

„ „ 90 „ „ „ up to 1 vol., in any proportion 

turbid in 3 
to 4 vols. 

*) Butt. Imp. Inst. 18 (1921), 342. — «) Chem. and Druggist 96 (1922), 56. — •) Holland and her CoUmies 
1 (1921), No, 7, p. 15. — *) Bull. Boure-Bertrand Fits, April 1921, 18. — *) In this case the acetylation is 
of very little importance, as patchouly alcohol cannot be acetylated quantitatively. 



56 Report of Schimmel S Co. 1922. 

Both samples had a very fine odour, thus distinguishing themselves from the 
Penang (Singapore) oils. The high specific gravity seems to indicate that the plant, 
from which they originate, belongs to the Singapore variety*). 

Two patchouly oils of 1917 and 1919 from the United Provinces of British India, 
examined by the Imperial Institute*), had the following properties: — dJU 0.992 and 
0.998, ttDwo ? and — 77 o nowo 1.513 and 1.515, soluble in 0.3 vol. of 90 per cent alcohol 
at 15^, acid v. 3.3 and 1.0, ester v. 4.4 and 5.3. It results from these figures that 
the oils have nothing in common with the Java oil and very little with that from 
Singapore, whereas they come very close to the distillates obtained in Europe from 
Singapore leaves. 

Peach Oil. — Although many preparations designated as "Peach OiF* or "Peach 
Essence*' have long been in use for flavouring purposes, it is well known that they 
consist for the most part of purely empirical mixtures of esters and essential oils 
with other aromatic substances which occur but little or not at all in the fruit whose 
flavour they are supposed to represent. This has been proved by F. B. Power and 
V. K Chesnut^) in their recent investigation of the odorous constituents of peaches. 
The authors used for their experiments the fresh pulp of selected ripe fruits (Georgia 
Belle), carefully deprived of the pits. This material w^s subjected to distillation in 
various quantities (106.6, 108.4, 120.2 and 14.18 kos.), but each time in one operation 
and without any added water, in a current of steam. The amount of distillate col- 
lected was about 65 liters in the three first cases and 12 liters in the last test. This 
liquid was repeatedly cohobated until the odorous substances were concentrated in 
volumes of 4.2, 2, 2 and 0.5 liters, respectively. From one such concentrated distillate 
the authors obtained by repeated extraction with ether 0.00074 per cent, of essential 
oil. In another case, when 155.6 kilos of peaches were distilled and the whole 
distillate extracted with ether, the yieid of essential oil was 1.2774 grams = 
0.0(X)82 per cent. The oil obtained was limpid, pale yellow and possessed an ex- 
ceedingly fragrant, intense peach-like odour. When cooled somewhat below the ordinary 
temperature, it formed a concrete transparent mass, which was interspersed with 
small acicular crystals, the latter evidently consisting of a paraffin hydrocarbon, melt- 
ing at 52°. The essential oil from peaches is very unstable. When exposed to the 
air, it becomes converted into a black, viscid mass and loses completely its original 
fragrance. Qnly when kept in a hermetically sealed glass tube, it appeared to remain 
unchanged. The oil probably consisted in the main of the linalyl esters of formic, 
acetic, valeric and caprylic acids, together with a little acetaldehyde and furfural, the 
latter having doubtless been produced during the process of distillation by the action 
of the organic acids on the sugar contained in the fruit. The presence of cadinene, 
or a compound giving a similar colour reaction (red colouring with glacial acetic and 
concentrated sulphuric acids), was also indicated. 

In order to prove the presence of linalool, the authors saponified 2 litres of the 
concentrated distillate with 25 grams of pure sodium hydroxide and distilled the 
saponified liquid, collecting about 800 cc. of the distillate. By extraction of this liquid, 
which smelied of linalool, with ether, 0.2620 grams = 0.00024 per cent, of a yellowish, 
oily residue were obtained, containing a small amount of solid substance, probably 
a hydrocarbon. Oxidation of the oily residue (linalool) lead in the end to a yellowish 



*) Comp. also Gildemeister and Hoffmann, The Volatile Oils, 2"<* edition, vol. Ill, p. 571. — «) Bull. Imp. 
hist. 18 (1920), 346. — •) Joum. Americ. chem. Soc. 48 (1921), 1725. 



Commercial and scientific notes on essential oils, 57 

oil, which had the pronounced odour of citral. On the addition of Schiff's reagent, 
it soon developed a purplish colour and it rapidly reduced an ammoniacal solution 
of silver oxide. A further identification of the, citral and, consequently, the linalool, 
was not possible, the available quantities being too small. 

The authors proved further that the saponified distillate, extracted with ether, 
contained -very small quantities of methyl alcohol (oxidation with potassium per- 
manganate led to formaldehyde). The acids were characterized by their silver salts; 
the aldehydes (acetaldehyde and an aldehyde of higher molecular weight) were prepared 
from the bisulphite compounds. 

In a similar way as in their investigation pf the odorous constituents of apples'), 
the authors proved that the aromatic substances of peaches contain traces of acet- 
aldehyde, even if prepared without the assistance o! heat 

No trace of hydrocyanic acid or benzaldehyde could be detected in the distillate 
from peach pulp. It may therefore be concluded that amygdalin is resh-icted to the 
kernels of the fruit. 

Peppermint Oil, American.— Although the use of American peppermint oil is 
almost out of the question now in Germany, owing to tremendous rate of exchange 
for the dollar, we were nevertiieiess able to purchase small quantities of .our well- 
known .brand "F. S. ^ Co.", as abroad; especially in the neutral countries, there are 
a good many customers for it, who only reluctantly would use another quality instead. 
Under the influence of the large stocks from 1920 and the general depression in the 
United States, last year's price of ,f 5.75 per pound of good crude oil was no longer 
to be maintained. The market gave way quickly, especially after the 1921 crop had . 
shown the splendid result of 350000 lbs., so that it was possible in the end to buy 
'• * ' .50. This figure attracts the attention of the speculators and it is the talk already 
that producers and dealers, who already last winter tried everything in order to 
nt the article from declining any further, will not allow the control of the stocks 
iss out of their hands. The quantities available were rather important towards 
nd of 1921 and as the 1922 crop will very probably also give a good result, one 
reckon with a continuance of the present low prices, at least for the near future, 
.es, a considerable enlargement of the peppermint fields in the West is to be 
:ted, as other agricultural products promise still less benefit for the time being. 
absence of the regular German demand makes itself keenly felt, of course, but 
rig as France and England do everything in order to damage our political economy 
o reduce the buying power of our money, it is not to be thought of a recurrence 
e former export of American peppermint oil to Germany. 

fhe fiftieth anniversary of the day of their firm's foundation (August aS*, 1871) 
induced our New York friends, Mess" Fritzsche Brothers, Inc., to ask their 
sentative in the peppermint districts for an extensive historical report covering 
>erJod of 50 years. It contains a good many important data concerning the 
opment of the peppermint oil industry in the United States and we copy some 
e details which might interest our readers. 

[lie cultivation of peppermint in the West started as far bach as 1852 to 1854, 
e County of St. |oseph in Michigan, llie distillation took place especially in the 
s of Florence, Sherman, and Lockport. In the years from 1858 to I860, there were 
t 10 farmers who grew peppermint, each about 30 to 50 acres of hilly land. The 

■) Comp. BeriM (German) 19£1, 7. 



58 Report of Schimmel § Co. 1922. 

yield was then from 25 to 30 lbs. of oil in the first, 18 to 20 in the second and 12 
to 15 in the third year. The prices ranged in 1852 to 1854 between $ 2.50 and $ 3.50 
per lb., the total production being perhaps about 25000 lbs. per year. The system of 
distillation differed little from the present one, only that then the stills were smaller. 
Up to 1860 the chief district for peppermint was Wayne County in the State of New 
York, but later on the importance of the Michigan peppermint fields grew rapidly. 
Towards the end of the seventies, one started there the cultivation in lower, well- 
watered districts (marshes) which were easier to work and keep free from weeds. 
Little by little, the Michigan growers acquired a monopoly, as their costs of production 
were lower than those of their colleagues in the State of New York. English peppermint 
plants were first introdued in 1892 and cultivated in thee neighbourhood of Nottaway 
in the County of St. )oseph. This proved to be a complete success, as the -English 
plants are more hardy than the American ones and yield almost twice the quantity 
of oil. After a short while, the American plants had been replaced almost completely 
by the English ones, and only in the neighbourhood of Charlotte in the State of Michigan, 
there are still some plantations of* the pure American varfety. The bad yield in oil ^^ 
indicates at once where both varieties are mixed. The cultivation of peppermint in 
Wayne County (New York) has ceased altogether. 

According to Magnus, Mabee and Reynard, Inc.*) the peppermfnt oil of the last 
crop shows an exceptional rotatory power ("dwo — 17 instead of —23°) and contains 
but little menthol. 

E. R. Kremers*) obtained by cohobation of the watery distillate of American Mentha 
piperita three fractions of the followir^g properties:— d24o 0.916 to 0.940, nD^o 1.468 to 
1.476, ester v. 21.65 to 29.9, ester content 7.7 to 10.6 per cent, alcohol as. ester 6.0 to 
3.3 per cent, ester v. after acetylation 195 to 160.5, total alcohol 63.6 to 50.8, free 
alcohol 57.6 to 42.5 per cent. The chief components were menthol (preparation of 
pure menthol, without any indication of the constants) and menthone (semicarbazone, 
m. p. 185°. Menthyl ester and 1,3-methylcyclohexanone (b. p. 169°, d2io 0.915, n^ 1.4430, 
semicarbazone, m. p. 180°) were present in small quantities. 

As to the history of peppermint oil in America, see page 105 of this Report, 

Peppermint Oil, Italian, — G. Micheletti*) communicates that tfiis year's pepper- 
mint crop in Italy (Vigone, Pancalieri, Piemonte) is satisfactory. 30000 kilos of oil 
were obtained, a quantity superior to last year's result The quality was also better. 
The menthol content exceeded 50 per cent on an average. 

Peppermint Oil, Japanese. —The lack of demand, characteristic of the )ap'anese 
peppermint market during the first months of the year covered by this Report^ would 
certainly have lead to a reduction of the prices in the course of the summer, if not 
'Speculators had done everything to hold them and even send them up, if possible, 
by means of extensive advances of money granted by the banks. They succeeded in 
bringing about a temporary firmness of the market in autumn, but under the influence 
of the new crop and the considerable old stocks the opinion seems to. prevail in the 
quarters concerned that a fall of the prices is not improbable in the near future, 
unless unforeseen events prevent it. The stocks in Japan about the middle of February 



1) Oa, Paint and Drug BepoHer 100 (1921) N© 17, 31. — «) Joum. Americ. Pharm. Assoc. 10 (1921), 835. 
•) Parfum. modeme U (1921), 215. 



^ 



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? 



Commercial and scientific notes on essential oils. 



59 



\ 



are said to have been 6200 cases of menthol and 7100 cases of peppermint oil, so 
that it seems to be only a question of time when the holders will come down with 
their prices, in order to revive the demand. The Japanese refiners also keep back with 
their purchases of crude oil, limiting themselves, as it seems, to satisfy what little 
demand there may be out of their old stocks. The quantities mentioned above 
represent about 700000 lbs. of oil, to which the rather considerable stocks in London, 
New York and Hamburg have to be added. It has generally been possible of late to 
buy much cheaper in London than in the producing country. 

The Japanese export statistics, rectified of late, give the following figures for the 
last 13 years:— Peppennint Oil 

1909 151 800 kin to the value of Yen 466600 

1910 146200 

1911 172400 

1912 184900 

1913 282100 

1914 277760 

1915 341200 

1916 360700 

1917 259700 

1918 214700 

1919 409199 

1920 321300 

1921 245400 



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1017700 


232900 


818800 


269300 


697400 


323500 


844500 


386500 


593600 


251200 


539700 


237500 


1307113 


239973 


1848000 


363400 


558413 


229900 



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Menthol 

102400 kin to the value of Yen 490500 

648800 
963200 
1589700 
2872800 
1816100 
1851000 
2410600 
1594300 
1554000 
2546898 
5417000 
2172480 



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The diagram here inserted has been sketched and kindly placed at our disposal 
by Mr. K. Kobayashi. It gives an idea of the prices paid for menthol and peppermint 
oil in the years from 1901 to 1920. The blue dots represent the menthol, the red 
ones, the peppermint oil ; ''o" means nominal quotation, no business having been done 
at the figure, whereas in the cases marked **•'' actual sales resulted. 

Specially striking in the diagram are the periodical rises of the quotations, for 
peppermint oil in the years 1902/03, 1912/13 and 1919/1920, which did not last very 
long, however. Whereas the high prices of 1902/03 were due to precipitated purchases 
of the American Government*), those of 1912/13 to the bad crop*), the last quite extra- 
ordinary rise can only be looked upon as a consequence of the war. 

R. E. Kremers^) investigated the oil obtained through cohobation of the distillation 
water of the Japanese peppermint. It had the following properties: — dwo 0.938, 
nDi80 1.485, ester v. 39.2, ester v. after acetylation 69.1, ester content 13.8 per cent., 
alcohol as ester 10.9^ total alcohol 20.3, free alcohol 9.4 percent. It was impossible 
to establish the presence of menthol, whereas the fractionated distillation yielded 
a product composed almost entirely of pulegone (nitroso derivative, m. p. 83^, semi- 
carbazone, m. p. 167°). 

Pimento Leaf Oil. — On page 76 of our last Bericht (German), we quoted a com- 
munication from an English source, according to which it was possible to obtain 
100000 lbs« of pimento leaf oil annually in Jamaica. The original paper ^) now before 



1) Conip. Report April 1903, 60. — «) Ibid. April 1912, 99. — «) Joum. Americ. Pharm. Assoc. 10 (1921), 
834. Comp. also the water oil of the American peppermint and of Monarda fistulosa, pages 58 and 50 of this 
Report. — *) Commerce Reports, No 257 of November !•♦, 1920. 



60 Report of Schimmel S Co. 1922. 

us states that the trials of preparing oil from the leaves are still going on in the Government 
Laboratories of Jamaica. The production on a large scale was not yet possible. It is 
further s^id that experiments had shown the pimento leaf oil to contain 1.8 per cent, 
eugenol, from which it would be possible to prepare to' advantage isoeugenol and vanillin. 

Pine Needle Oils. -^ A comparative investigation of Eastern and Western hemlock 
oils has been started by D. E. Cable ^). Five oils originating from the East (Michigan, 
Wisconsin, New Hampshire, Tennessee, Virginia) which were distilled during the 
months of June, July, and August from the stripped leaves of Tmga canadensis, Carr. 
with a yield of 0.29 to 0.65 per cent., show,ed the constants: — dfg| 0.9020 to 0.9234, 
Wd»o —14.80 to — 21.650, newo 1.4691 to 1.4704, acid v. 0.33 to 0.70, ester v. 103.8 to 
147.35, ester v. after acet. 113.5 to 171.94, esters calc. as bornyl acetate 36.33 to 
51 .57 per cent, total borneol 31 .24 to 47.41 . The Wisconsin oil excelled by its high 
content of esters and of total borneol. 

Three oils from Western hemlock, originating from Coeur d'Alene, Idaho, behaved 
quite differently. They were distilled in the months of May, June, and July 1920 from the 
stripped leaves of Tsuga heterophylla, Sargent (yield 0.32 to 0.36 per cent.) and showed the 
constants as follow:— d^g 0.8444 to 0.8521, Mdwo— 6.74 to —20.00°, nD»o 1.4790 to 
1.4840, acid v. 2.57 to 3.4, ester v. 6.7 to 17.25, ester v. after acet. 19.6 to 33.4, esters 
calc. as bornyl acetate 2.35 to 6.02 per cent., total borneol 5.43 to 9.24 per cent. 

For the purpose of comparing these oils with ordinary commercial hemlock oils 
of the years 1909 and 1919, the following constants for three oils of commerce were 
ascertained:— dj~ 0.9190 to 0.9664, [alowo — 14.85 to — 24.85 o, nojoo 1.4721 to 1.4786, 
acid V. 1.51 to 18.45, ester v. 105.09 to 115.41, ester v. after acet 149.51 to 150.83, 
esters calc. as bornyl acetate 36.78 to 40.39 per cent., total borneol 41,55 to 41.74 pfsr cent. 

The last-named oils are remarkable on account of the extraordinary high upper 
values for density, tefractive index, and acid content indicating, partially, resinification. 

The essential oil of the needles from Pintis sUvestris, L. of Russian origin has 
hitherto been investigated only by Hirschsohn*) and, later on, by J. Schindelmeiser^). 
According to this author, Russian pine needle oil constitutes an oil with a pleasant 
aromatic odour, showing the constants :— b. p. 160 to 250 o, diso 0.875, a + 0- On 
fractionated distillation from 10 to 10° the following fractions resulted:— 160 to 170°, 
48 per cent; 170 to 180° 32 per cent; 180 to 190° 12 per cent The first fraction was 
optically active (aD + 2°30') and contained d-pinene; nitrolamine, m. p. 118^. The 
fraction 170 to 180° was laevorotatory (ao — 2°46') and contained, in the opinion of 
the author, equally as the fraction 180 to 190°, Mimonene in addition to some 
ri-limonene (tetrabromide of the total limonene, m. p. 125' to 126°, dihydrobromide 
of the total limonene, m. p. 64 O; cf. the constants of the corresponding dipentene 
derivatives). The fraction boiling above 190° contained inactive borneol (phenyl- 
urethane, m. p. 137 to 138°) and, probably, some cadinene (dihydrochloride, m. p. 117 
to 118°). Hence, the oil resembled in its composition, apart from the absence of 
sylvestrene, the German and the Swedish pine needle oils*). 

Quitcli Root Oil. — It is little known that quitch root (Triticum repens. L.) contains 
an essential oil. A trial distillation of selected roots from Miltitz fields yielded 



») Joitm. Americ. pharm. Assoc. 10 (1921), 170. — «) Pharm. Zeitschr. f. Russland 481 (1891). — ») Sitz.- 
Ber. d. Naturforscher-Oes. &. d. Universitdt Jurjew (Dorpat) 18, 2 (1903), 315. — *) Cf. Gildemeister and 
Hoffmann, The Volatile Oils, 2"<' edition, vol. II, p. 122 and Bericht (German) 1920, 35. 



i 



i 



--*> 



/ 



Commercial and scientific notes on essential oils. 61 

* 

0.0065 per cent, of a dark brown distillate of feebly aromatic, somewhat sweetish 
odour; dwo 0.9665, acid v. 36.2, ester v. 29.0, incompletely soluble in 10 Vols, of 
^ per cent, alcohol. Rotation and refraction could not be determined on account of 
the dark colour of the oil. 

Another batch of quitch roots, mixed with tarragon roojs, however, yielded 
0.052 per cent, of essential oil of light brown colour: — diso 0.9670, "d +2^30', 
noMo 1.55359, acid v. 5.4, ester v. 10.6, incompletely soluble in 10 vols, of 80 per cent, 
alcohol, soluble in 2 vols, and more of 90 per cent, alcohol. 

» 

Ravensara Oil- — The leaves and young twigs of Ravensara aromatica, J. F. Gmel., 
a lauracea growing on the high plains of Madagascar, yielded on distillation with steam 
an essential oil of an agreeable, camphor-like smell. It reminded one of eucalyptus 
oil and consisted, according to Ferrand and Bonafous^), of a terpene mixed with an 
oxygenated body. . 

Roman Chamomile Oil. — According to Massera^), the oil contained in the flowers 
of Roman chamomiles to the extent of 0.8 to 1 per cent, had the following constants :-»- 
d 0.905 to 0.920, [a]D —3° to +3°, sap. v. 220 to 320, soluble in less than 1 vol. and, 
with slight turbidity, in 3 vols, of 70 per cent, alcohol. In addition to the components 
enumerated by the author (i^obutyl and i^oamyl esters Of angelic and tiglic acid, 
anthernol and anthemene), azulene is present, besides, according to Blaise, ^i-butylic 
alcohol and, according to van Romburgh, also /^-methylethylpropylic alcohoP). 

Rose Oil, Bulgarian. — The estimations of the 1921 crop vary between 1200 and 
1500 kilos. Although these quantities do not come up by for the average pre-war 
results, they are about 20 per cent, better than last year*s result. This excess has not 
had any effect on the prices, however, and the market remained almost unaltered. It 
was remarkable to what an extent the illegitimate trade with rose oil has grown. It is 
understandable that the important banks are greatly interested in transactions concerning 
such a valuable commodity and that even the State may now and then sell certain 
important lots^ last year, however, rose oil was offered from many other quarters, 
which have but little or nothing at all to do with the distillation of otto of roses. The 
number of such sellers, who often carried their goods about with them in handbags, 
was specially large, among them a good many Bulgarian students, who meant to earn 
like that the means necessary for continuing their studies at German universities. It 
is- desirable that these after-effects of the war should disappear quickly, to the benefit 
of the legitimate trade. Many a buyer who was not in a position to test the "bargain" 
offered, has been done in such transactions. 

T. H. Shipkoff*) publishes an article on the Bulgarian rose industry, from which 
we copy some data, as far as they are not contained in our previous Reports^), The 
district in Bulgaria, caUed by all western travellers *The Land of the Roses", extends 
over that portion of the southern slopes of the main Balkans mountains, which comprises 
the whole branch range of Stredna Cora (Little Balkans). Its average length is about 
80 miles and its average with about 30 miles ^). The average elevation of the rose 
district is bout 1300 feet above the level of the sea, and the average height of the 



1) ParfUm. modeme 14 (1921), 100. — «) Bev. Ital. d. Esaenze e ProfUm. As per Peifum. Record 12 (1921), 
283. — ») Comp. Gildemeister and Hoffmann, The Volatile Oils, 2"<* edition, vol. Ill, p. 616. — *) Americ 
Perfumer 16 (1921), 48. — *) Comp. Beports April 1908, 86; April 1918, 89; 1916, 47. — «) Com>. Gildemeister 
and Hoffmann, The Volatile Oils, 2nc edition, vol. II, p. 552, map. 



.». . 



62 , Report of Schimmel S Co. 1922. 

main Balkans in the north is about 5600 feet, while the average height of the Little 
Balkans is about 3700 feet. There are over 180 communities or villages with more than 
21 000 small proprietors of rose gardens owning on an average about one acre each. Only 
about half of the 14000 small native stills, existing in the country, are still in use, for 
during the last years before the great war, 12 modern distilling plants have been built. 

Whereas this industry had developed steadily up to the Balkan war in 1912, it 
decreased continuously from that time. The consequences of the hard years of war 
are still felt and other agricultural products have taken the place of the roses, although 
the demand for otto of roses has trebled of late. From 1889 to 1912 the area planted with 
roses increased from 7500 to 30000 acres, yielding on an average up to 27000000 lbs. of 
roses, from which 3600 to 4000 kilos of rose oil were obtained. The record crops of 1900 and 
1907 yielded even 30000000 lbs. of flowers each, or about 175000 ounces of otto of roses. 

The present area cultivated with roses will hardly exceed 14000 acres and the yield 
of oil has also gone down, as the rose gardens have been neglected and not sufficiently 
manured. The quantity of oil produced went down from 4000 kilos in 1912 to 2410 kilos in 
1917, 1840 in 1918, 1600 in 1919, 1200 in 1920*) and for 1921 only 1000 kilos are expected. 

Prior to the war, the exports were as follows: — 

Destination 1900 , 1906 1911 

France ..... 1548 kilos 2607 kilos 1483 kilos 

United States ... 849 „ 1524 „ 525 „ ^ 

Germany 568 „ 1113 „ 1595 „ 

Great Britain ... 1175 „ 1074 „ 572 „ 

Russia 202 „ 278 „ 158 „ 

During the war, nothing was exported to the United States, France, England and 
Russia, whereas Germany imported annually 1700 kilos, Switzerland about 600 kilos, 
Austria about 200 kilos, together with Holland. Since the war is oyer, the American 
market has been the most important by far. In 1919, 3500 kilos were exported to the 
United States, 900 kilos to France and 400 kilos to England*). The exports to Germany 
are supposed to have risen considerably in 1920. 

Rosemary Oil. — On Spanish oil of rosemary, see page 106 of this Report. 

Sandalwood Oil, East Indian. — The Department of Statistics in India publishes 
the following statement showing the exports of sandalwood oiP): — 

January 1921 Ten months, April 1920 to January 1921. 

Countries of final destination Quantity Value Quantity Value 

Great Britain 6237 lbs. 155925 Rs. 109652 lbs. 2745600 Rs. 

France 2930 « 69000 „ 5030 „ 125000 „ 

Straits Settlements ...— — 190„ 2300,, 

Ceylon — — 4 „ 275 „ 

Hong Kong 720 „ 4320 „ 1290 „ 8880 „ 

Asiatic Turkey .... — — — 15 „ 

Java ........— — 980 „ 20300 „ 

Portuguese East Africa . — — 2 „ 40 „ 

Egypt . - — 1 190 „ 32825 „ 

Australia . — — ' 100 „ 2 150 „ 

Total 9887 lbs. 229245 Rs. 118438 lbs. 2937385 Rs. 



^) It is stated officially that the 1920 crop yielded only 900 kilos, comp. Bericht (German) 19S1, 39. ~ 
*) These figures, compared with those given for the actual production of rose oil, confirm the well-known fact that 
Bulgarian Otto of Roses is exported only with the usual addition of palmarosa oil. — *) Perfitm. Record 12 (1921), 180. 



Commercial and scientific notes on essential oils. 63 

In the report on the Administration of Mysore^) for the year ending June last, it 
is stated that the sandalwood oil factories dealt with 1362 tons of sandalwood. The 
demand for the oil was good, but the profits were small, as the priced of the wood 
had been driven up very high in the Coorg and Madras aucjtions. 

As the Dutch East Indies export sandalwood and on the other hand import about 
1000 lbs. of sandalwood oil annually from British India, the Government intends to 
produce it in the country. A question still to be solved would be the cutting of the 
wood into chips, in which direction experiments are going to be made. Out of 37 kilos 
of sandalwood 1023 cc. = 2.6 per cerkt. of oil have been distilled^). The plan seems 
to have come to nothing, however, for according to a report of the Dutch Chamber 
of Commerce in New York") the distillation of sandalwood oil in Java, begun during 
the war, has been given up again, as being'unprofitabte. 

E. |. Parry*) communicates that during the last years he frequently received from 
reliable French or English (Indian) distillers sandalwood oils which were fit for use in 
perfumery but the constants of which did not comply with the requirements of the 
British Pharmacopeia. In his opinion, the distillation in such cases had either been- 
incomplete or too slow. Parry proves experimentally that a prolonged action of steam 
on the oil altered the constants, reducing in particular the optical rotation. 

We would add that this is nothing new, for we have pointed out years ago**) that 
the decomposition products, which easily form during the distillation, alter the properties 
of the oils and that only a very careful distillation will yield a normal product. 

Sandalwood Oil, West Indian. — Large quantities of wood have arrived of late 
and we hope to be able before long to supply fresh oil on a larger scale. 

Oil of Saturela montana. — By steam-distillation of the not yet flowering dry herb 
of Satureia montana, L, gathered in June in the Italian province of Aqqila, P. Leone and 
E. Angelescu^) obtained 0.69 per cent, of a yellow of strong aromatic smell and burning 
taste. By extraction of the herb with acetone and distillation of the extract with steam, 
the authors obtained 1 .63 per cent, of an oil which had the same specific gravity and 
the same phenol content as the former. It is to be supposed, in consequence, that 
the dry herb contains in realty at least 1,63 per cent, of oil. — The oil had the following^ 
properties:— d^ 0.9053, Wdmo — 3.05° nnwo 1 .49926, acid v.2.22, sap.v.6.75, esterv.4.53, 
corresponding to an ester content of 1 i58 per cent (calculated as linalyl acetate), carvacrol 
content 28 per cent, (nitroderivative, m. p. 77 to 78°; determined through shaking with 
a 5 per cent, soda lye). The oil freed from the phenol contained 10 per cent, of an> 
alcohol, which has not been identified more closely (sap. v. after acet. 54.3) and yielded 
the following fractions on repeated distillation under normal pressure: — 1. b. p. 170 to 
180O (54 per cent.), 2. b. p. 180 to 190° (12 per cent., 3. b. p. 190 to 205° (8 per cent.), 
4. b. p. 205 to 232 o (6 per cent.), 5. b. p. 232 to 252 o (12 per cent). After having been 
boiled for five hours with metallic sodium, the first and second fractions yielded other 
fractions boiling at 173 to 175° (38.1 per cent.) and at 176 to 178° (20.3 per cent),, 
consisting of cymene (hydroxywopropylbenzoic acid, m. p. 156 to 157^) and dipentene 



1) AmeHc. Perfxtmer 16 (1921), 107. — «) Chemist and Druggist »4 (1921), 406. — «) Holland and her 
colonies 1 (1921), No. 7, p. 15. — *) Parfum. mqderne U (1921), 54. — ») Comp. Seport April 1908, 92. — 
(» Gazz. chim. ital. 61 (1921), IL 368. 



^4 Report OF SCHiMMEL S Co. 1922. 

(nitrolbenzylamine, m. p. 108°), respectively. The original oil, therefore, contained abou 
21 per cent of cymene arid 14 per cent, of dipentene. 

The oil of the French plant has been investigated already years ago by several 
authors. A. Haller found in it 35 to 40 per cent, of carvacrol. According to our 
determinations an oil from Barreme contained about 27 per cent, and one from Sault 
about 32 per cent, of carvacrol*). 

Oil of Sklminia laureola. — The oil of SJdmmia laureoh, Hook, fil., on whose 
origin and properties we gave a short notice p. 46 on of OMr last Bericht (German ed.), 
has recently been investigated by J. L. Simonsen*). On distilling the shade-dried 
leaves collected in the Chakrata Division during June and early July, the author obtained 
about 0.6 percent of a pale emerald-green oil'with the following constants: d^| 0.9041; 
noaoo 1.4648; acid v., 3.63; sap. v. 197.36; sap. v. after acet. 238.6 (prior to acetylation 
the oil was mixed with turpentine oil)'). After washing the oil with dilute alkali, the 
oil was repeatedly fractionated under 200 mm. pressure and the following fractions 
were obtained:— 1, B. p. 130 to 140°, 0.46 pier cent.; 2. 140 to 145°, 4.6 percent.; 
3. 145 to 150° 0.61 percent; 4. 150 to 155° 8.4 percent; 5. 155 to 160° 2.3 percent; 
•6. 160 to 167°, 2.0 percent; 7, 167 to 173° 50 percent; 8. 173 to 177°, 0.61 percent; 
^. 177 to 182°, 1.05.per cent; 10. 182 to 190°, 1.2 per cent; 11. above 190° 18.2 per cent 

The first three fractions contained a hydrocarbon boiling at 130 to 135° (200 mm.) 
or 176 to 182° (695 mm.); d|| 0.859; Wdwo — 4.11°; nnaoo 1.471), the nature of which 
remained undecided. Fraction 4 consisted of nearly pure Minalool (phenylurethane, 
m. p. 65°). The fractions 5 to 9 contained partly Minalool, partly Minalyl acetate, 
partly a mixture of both. In addition, fractions 8 to 10 contained a high-boiling alcohol. 
From fraction 11, repeated distillation yielded unpleasently-smelling oils, possibly 
mixtures of sesquiterpene alcohols and esters. 

Hence, the oil investigated consisted in the main of Minalyl acetate, furthermore 
of Minalool, a hydrocarbon and a mixture of sesquiterpene alcohols and esters. 

Spearmint Oil. A sample of the entire dried plant of Mentha longifolia (Host, 
or Hudsi?) collected in the Somerset East district of the Cape Province and consisting 
of leaves 40 p. c, and loose stalks 60 p.c., was examined at the Imperial Institute^) 
The stalks were found to be practically free from volatile oil, the leaves yielded on 
steam distillation 2.4 per cent oil, equivalent to a yield of 0.98 per cent from the 
entire original sample. The colourless oil had the characteristic odour and taste of 
spearmint oil and the following constants:— dj^ 0.947; rtj)—- 47.6°; n^ 1.4925; ketones 
{estimated by sulphite method), calculated as carone, 70 percent The oil from this 
sample of spearmint resembled the oils from Mentha spicata, Huds. and of Mentha 
viridis, L, but contained a very high percentage of ketones and corresponded in this 
respect with the Austrian spearmint oil. 

Spike Oil. — As to Spanish spike oil, see page 106 of this Jteport, 



*) Comp. Gildemeister and Hoffmann, The Volatile Oila, 2"" edition, vol. Ill, p. 470. — *) Joum. Soc. chem. 
Ind. 40 (1921), T. 126. — ») The above constants differ considerably from those found by Roure-Bertrand Fils 
(comp. Bericht 1921, p. 46). With a leaf oil forwarded to us we ascertained the following characters:— diso 0.8876, 
ajj -f 2 o 22', nDH)0 1 .47260, acid v., 0, sap. v., 128.8 = 45.1 per cent, of esters, calculated as linalyl acetate ; soluble 
in 0.2 vol. 90 percent, ^cohol, \*ith more than 1.3 vol. strong opalescence. The colourless oil showed a bluish 
fluorescence and recalled the odour of petitgrain oil. It was said to originate from Skimmia laureola, Sieb. et 
Zucc. {Limonia laureola, D.C.), Roure-Bertrand Fils state Skimmia laureola, Hook, fil., which name we fail to 
iind in the Kew Index. — *) Bull. Imp. Inst. 18 (1921), 350. 



Distillation of Essential Oils in Spain. 



Commercial and stiENxiFic notes on essential oils. 



65 



Maximum 


Minimum 




6/0 


' .4/9 


1916 


6/11 • 


5/6 


1917 


7/3' 


6/3 


1918 


6/3 


5/0 


1919 


4/9 


3/0 , 


1920 



Maximum 


Minimum 


3/6 


' ■ 3/2 . 


4/6 


3/3 


6/2 


4/0 


6/0 


4/2 


6/0 


3/6 



Staranise Oil. — The following statistics of maximum and minimum prices of 
staranise oil are taken from an English periodical *):^- 

1911 ; . . 

1912 . . . 

1913 . . . 

1914 . . . 

1915 \ . . 

As 'it is shown, the maximum pre-war prices have not been reached again, in spite 
of the universal depreciation of the money. Although in November 1921 the price went 
down a;s far as 2/2 per lb.*), it was believed that this was not the lowest yet, for there 
were considerable stocks and little demand. In 1921 » 4000 cases of 66^/3 lbs. each 
arrived in London, where abundant stocks existed already. Tbe oil was imported 
partly in exchange for textiles. , 

It is further stated that formerly there was a good market for staranise oil, chiefly 
for liqueurs and confectionery. Nowadays the Russian demand is missing and France, 
Germany and the United States require but little. In the latter country, the decrease 
in the demand for staranise oil is ascribed to the prohibition of alcoholic drinks. The 
best consumers of the articles are now most likely Spain and South America, but it 
is expected that the French and English demand will increase again. 

Oil of Tagetes anisata. — The fresh herb of Tagetes anisata, LiWo^ n, sp., 3i com-; 
posita growing in the pampas of Argentina at an elevation of from 1000 to 3000 m., 
yielded on steam distillation, according to F. Zelada®) 0.7 to 0.8 per cent, of a green oil. 
The product' resembled anise oil and had th^ following propertied: b.p. 214 to 218°, 
solidification p. —60, dieo 0.9862, «—loioVn 1.5432, ester v. after acetylation 23.4, sap. v. 3.1, 
iodine V. 158.5, alcohol as CieHisO 0.852 per cent, ester as CieHnOCOCHs 1 .082 per cent, 
total alcohol as CieHisO 3.229 percent^ soluble in 5 vols, of 90 per cent alcohol*). 

Tarragon Root Oil. — See Estragon root oil, p. 34 of this Report. 

Thyme Oil. — The Spanish oils of thyme are of different composition and may be 
grouped in oils containing thymol, carvacrol, or citraL The same division could be 
used for th^ manifold species of Thymus occurring in Spain. According to the 'few 
existing authentjcal indications concerning the botanical origin of the Spanish thyme 
oils, there seems to be a certain conformity in the characteristics of the plants belonging 
to one and the same of the groups mentioned. According to Rubeck and E. H. Holmes*), 
Thymus vulgaris, L., and Thymtis Zygis, L, which are much alike and are both known 
in Spain by the name of tomUlo sals&ro, being used as pot-herbs, certainly belong to 
the first group. Thymus hyemalis, Lange, according to Holmes the mother-plant of 
the so-called Spanish verbena oil, is closely allied to Thymus hirtm, Willd. ftomillo 
limoneroj; both kinds contain citraP). The similarity appears to be less striking (the 
relative indications in books, etc. are very scanty) between Thymus Mastichina, L, 
(tomUlo bianco) and Thymus cephdlotus, t., the oils of which according to Dorronsoro') 



») Chemist and Bruggiat 95 (1921), 631. — «) Com. BeHtM (German) 1921, 46. — ») Parfum. modeme 
14 (1921), 32. — *) There seem fo be grave discrepancies between the acetytation and ester values and the 
amount of alcohol, etc. calculated. Besides, CieHigO seems to stand for CioHisO. — *) Ferfuim. Record 11 
(1920), 339. — •) Cf. Berieht (German) 1921, 87. — ') Comp. Jfepor* April 1911, 111. 

5 



66 



Report of SchimmelSCo. 1922. 



contain about 60 per cent, of cineole. We do not know, however, what variety of Thynma 
plants contain the oils rich in carvacrol. Holmes may hp right in saying that Thymus 
Piperella, L., iind Tliymus ccespiticius, Hoffm., the popular name of which (pehrdla) in- 
dicates a sharp taste like pepper, belong to the carvacrol group. An oil distilled from 
the fresh herb of Thymus capitatus, Lk. (from Granada) .contained according to our 
own investigation 6 per cent, of thymol and a liquid phenol, perhaps carvacrol*). 

This is about all that has been recorded as to the exact botanical origin of the 
Spanish thyme oils. On the other hand it is known that more than 30 (Willkomm*) 
states 39) different kinds of Thymus are spread over the Iberian peninsula. They partly 
grow in one and the same district, have great similarity and are perhaps not always 
differentiated by the gatherers. . The thyme plants are gathered above all from the 
"tomUlares" (tomUlo = thyme) which are so characteristic for Spain and, with exception 
of the Morthatlantic zone of the peninsula, occur in the central table-l^nd as well as 
in the coast provinces and the lowlands along the Ebro, in South Aragon, Catalonia, 
Valencia, low0r Andalusia and Algarbia, covering enormous spaces of uncultivated 
land. These ''tomUlares" attain their largest dimensions in the table-land, along the 
Duero, on either side of the central mountain chain and in the East, South and South- 
west of New Castile. There are thyme, lavender, sage and rosemary heaths, named 
after the labiate that preponderates. C. Hartwich') gives a very good description of 
such a heath: — "On this waste ground of debris the plants grow isolated, though fairly 
close together, so that ihe naked soil can be seen everywhere in between. This is 
the reason why such stretches of land often appear absolutely bare froqi a distance. 
The dominating plants, as the name of the steppe indicates already, is a species of 
thyme (Thymus Zygis, L.). The plant forms round little shrubs, perhaps as large as 
a fist, sometimes, when a stem grows a little higher, miniature trees, Hke those we 
owe to the Japaqese art of gardening. ^ They have small, needle-shapea leaves, on 
which the golden-yellow oil glands can be seen through a magnifying glass, and are 
covered with tiny red flowers. A stem which I examined at home was nine years old." 

The Thymus species most frequently named and apparently also the most widely 
distributed in Spain are Thymus vulgaris, L, Thymus Zygis, L. and Thymus Mastichina, L. 
As E. M. Holmes*) determined, Thymus Zygis differs from the otherwise similar common 
thyme, as follows : — The bracts are larger than the ordinary leaves, the whirls of 
whitish flowerets frorti an uninterrupted spike and no axillary or terminal heads as 
with Thymus mdgaris. According to Willkomm*) the common thyme is to be found 
in Navarra, in the plain of Pamplona, along the Duero and the Iberian central mountain 
chain, in the Nord-West of Guadalajara and in the mountainous regions of Catalonia 
and Valencia, whereas Thymus Zygis occurs in the North of Old Castile, near Alar 
del Rey (Palencia) in the upland ol Murcia in New Castile, in the Vega of Granada, 
in the Sierra Nevada and in the uncultivated coast regions of the provinces of Cadiz 
and Huelva. — Thymus Mastichina grows on waste ground and by the side of paths 
and fields in- Cantabria, in the slate mountains of Asturia and Leon, in the northern 
table-land (togethej with Thymus vulgaris), in the lavender heaths of New Castile along 
the central mountain chain (together with Thymus Zygis), on sandy soil between Almeria 
and the Bay of Gibraltar, on the dry calcareous hills round Granada, and in the 
"fomillares** of the coast zone of Cadiz and Huelva (together with Thymus Zygis). Of 



^) Bericht October 1889, 56. — *) Engler, Die Vegetation der Erde.' Grundzuge der P/ianzenverbreitung 
auf der iheriichen Halbinsel. By R. Willkoram. 1896. — ') Spring holidays in Spain. Apotheker-Ztg. 21 {1906), 
842, — *) Loc. cit. — •) Loc. cit. 



Commercial and scientific notes on. essential oils. 67 

the other species the following are mentioned', ^r- Thymus hirtvs, Willd., which thrives in 
Central and southern Spafn, on the calpareous hills round Granada and in the lower 
regions of the Pinsapo Forest, Thymus hyem^is, Lange, " in south-eastern Spain, Thymus 
cephaloius, L, in Valencia, in lower Asturia and, according to Dorronsoro*) in Almeria, 
Thymus ccespiticus, Brot., in Estremadura and Galicia) Thymus Uperella, L., in Valencia 
on rocky slopes, Thymus x^pylloides, Bory, (Shmarilla) in the alps of the Sierra Nevada. 
To quite another, species belongs the so-called Andalusian thyme (TomUlo andaluz 
= fomUlo carrasqueno) or Gorydothymus, which according to Bias Lazaro*) is Corydo- 
thymus capitatuSy Rchb. B. Dorronsoro^) writes about it as follows: — "Various kinds 
of thyme are distilled in Spain, vizi, the tomillo corriente (common thyme) = tomUlo 
aceitunero (olive thyme) = Thymus vulgaris, L.,^ the tomUlo risquero (thyme of the rocks) = 
Thymus Zygis, L, the tomUlo sanjuanero (St. John*s - thyme) = Thymus hyemalis, Lg., 
and the tomUlo carrasqueno (holm-oak thyme) or tomUlo dndaluz (Andalusian thyme), 
which latter, however, is no real thyme, but Corydotkymus capitatus, Rchb., belonging 
to an allied species.^' * 

In August 1915, we examined in ovir research laboratory a Spanish oil from 
Barcelona, on whose botanical origin, unfortunately, nothing definite could be as- 
certained. Since^ only very little positive is known as to the chemical composition of 
the Spanish oils, the results of the following investigation gave no clue concerning 
the botanical source of the oil. Owing to the war, the work had unfortunately to be 
discontinued and was terftiinated only before long, when the oil had been left standing 
for nearly six years (protected from direct light) after having been fractionated and 
freed .from phenols by treatment with dilute caustic lye. 

The original oil showed the following constants: — diso 0.9297, «d+0°35', soluble 
in 3.5 vols, and more of 70 per cent.^ alcohol; phenols 45 per cent., for the greater 
part thymol. • 

The most volatile fraction of the b. p. 130 to 132^ smelled of amyl alcohol and 
gave the characteristic naphthylurethane, m. p. 51 to 52^ obtained by us on a previous 
occasion. In th6 fractions of b. p. range 132 to 150° we suspected owing to their 
amylaceous smell the presence of amylcarhinols. Since they consisted doubtlessly of 
mixtures, contaminated possibly with small amounts of amylic or similar ketones, we 
refrained from further isolation and identification. We only by way of experiment, 
succeeded in isolating a naphthylurethane, m. p. 47 to 48°. We were unable to prove the 
existence of a ketone, nor the formation of such by oxidation with bichromate solution. 
N A small fraction, l?.'p. 145 to 150° (diso 0.8495, «D+3°28',nD»o 1.45052), yielded 
on benzoylation with the aid of pyridine a benzoate, b. p. 134 to 135° (6 mm.), which 
on saponification gave rise to an alcohol with the characteristic odour of ^^y-hexenoL 
This alcohol had previously') been obtained by us in shape of its phenylacetate from 
the last runnings of Japanese peppermint oil. Although the oil showed the same 
boiling point (156°) as the above-mentioned alcohol, we were unable to raise the 
melting point of the naphthylurethane beyond 58 to 6.0°, whereas the derivative of 
the pure alcohol from peppermint oil melts at 72°. In spite of this discrepancy we 
do not hesitate .to accept the identity of the alcohol with ^,y'\\exeno\. A closer 
examination carried out with more material will in all probability confirm this identity 
and thus prove the existence of free /5,/-hexenol in Spanish thyme oil. 



^) Cf. Bericht (German) 1921, 87. -^ *) E8tud(o quimico de esencias natiirales espanolas. Madrid 1919> 
p, 134. — «) Report 1918, 39; Walbaum, Journ. f. prakt. Chem. II. 96 (1918), 245. 

5* 



>•»■■■" ♦ 



68 Report of Schimmel S Co. 1922. 

« 

In the next fractions we found after repeated, careful fractionation a new terpene 
with a carrot-like odour and the following constants : — 

1. B.p. 155^: . duio 0.8533, a© +4050', noao 1.46201 

2. B.p. 155^: - di8o 0.8535, «d + 40 58', nD»o 1.46221 

3. B.p. 155 to 1560: di5oO,g537, aD+40 35', nDioo 1.46231. 

The values obtained on combustion pointed to a terpene CioHw : — 

0.1822 g. substance gave 0.5879 g. C0», 0.1958 g. HgO. 

-Found Calc. for C10H16 

C 87.98 per cent. 88.23 per cent. 

H 11.93 per cent 11.77 per cent. 

Mol. refr. found calc. for CioHio/j' 
43.89 43.51. 

The nitrosochloride, purified by means of chloroform and methyl alcohol, shows 
a strong tendency to decompose and can therefore be prepared and purified only in 
small amounts. Decomposition starts at about 85^ in a yery sudden and violent 
manner. The piperidide melts at 194 to 195^, the nitrolbenzylamine indistinctly from 
105 to 108^; the anilide was not obtainable, neither a solid nitrosate. When dissolved 
glacial acetic acid and cooled down the terpene adds somewhat more than two atoms 
of bromine; the resulting bromide remains oily. Likewise, the hydrochLoride obtained 
by saturating, in glacial acetic acid solution, the terpene with hydrogen chloride gas 
was liquid. On trying to hydrate the terpene by action of acetic and sulphuric acids 
resinification resulted. When oxidized by means of permanganate solution, with 
cooling by ice (according to the method for obtaining pinonic acid), the terpene gave 
rise to a neutral oxidation product soluble in water and chloroform, which did not 
distil without decomposing ^d was therefore not yet obtainable in the crystalline 
state. On further oxidation with neutral permanganate at 100^ there was obtained, 
in addition to oxalic acid, m. p. about 100^, . and acetic acid (Ag estimated in the 
silver salt 64.20 per cent), an acid which decomposed on distillation in vacuo afid 
which evidently was not a ketonic acid. Treatment with dimethyl sulphate yielded no 
ester. Details as to the chemical structure of the terpene are to be expected only 
after closer investigation. We wish to add that this oil offered no clue for the presence 
of a-pinene, in contradiction to another oil which years ago^) we found to contain 
that terpene. Considering the great variety in the botanical origin of the Spanish 
thyme oils this different behaviour is by no means surprising. 

A very small amount of camphene is present in the Spanish oil.- It was identified 
by treating the fractions boiling above 157 ^ in the usual manner with acetic-sulphuric| 
acid, when a trifle of wobornyl acetate (b. p. 82 to 88° at 6 mm.; sap. value 202) was 
isolated by fractionation. The free i^oborneol obtained therefrom by saponification 
melted at 208 to 212°. 

/S-Pinene was likewise a constituent of the oil. After oxidising a fraction b.p. 165 
to 169^ with alkaline permanganate a hydrocarbon with the following constants was 
regenerated ; — b. p. 163 to 167° dsoo 0.8520, aD+3°45', noMo 1.46609, mol. refr. found 
44.02, calc. 43.5. On further oxidation with permanganate is yielded nopinic acid, 
m. p. 126 to 127°. The hydrocarbon occurs in minute quantity only. 

A Hydrocarbon fraction, b.p. 165 to 168° (diso 0.8567, aD+3°57', noioo 1.47141) 
which on saturating with hydrogen chloride gas and after some standing had yielded 



1) lieport October 1894, 57. 



Commercial and scientific notes on essential oils. 69 

terptnene dihydro chloride, m. p. 52°, was suspected to contain sabinene. However, 
on oxidation with alkaline permanganate solution, no sabinenic acid was obtainable. 

p-Cymene could be proved to be present only after many fruitless attempts, by 
oxidation of fractions b. p. 175 to 179° with strong permanganate solution, when 
«-hydroxywopropylbenzoic acid, m. p. 153 to 154°, was the result. On boiling with 
strong hydrochloric acid the difficultly-soluble propenylbenzoic acid, m. p. 160 to 161°, 
was formed. The amount of cymene present is exceedingly small. As far back as 
1856 Lallemand*) was able to prove the presence of j)-cymene in a thyme oil. However, 
it must remain an open question whether in this case an oil of different botanical 
origin was under investigation or whether the |)-cymene had been formed, by a 
secondary process, from terpinene, an Important constituent of the oil. . . 

y-Terpinene is the main constituent of the phenol-free oil and could be traced in 
all sub-fractions b. p. 176 to 183°. All of these fractions gave on saturation with 
hydrogen chloride gas in glacial acetic acid solution, an oily hydrochloride which 
either was precipitated by addition of water or was obtained on evaporation of the 
solvent in an open dish after some standing, and could be brought to solidification 
by strong cooling and additionally after inoculation. When crystallized from methyl 
alcohol the dihydro chloride melted at 51 to 52°, and in mixture with the corresponding 
derivative of dipentene very considerable depression of the melting point was observed. 
From various of the afore-mentioned subtractions there was obtained, on oxidation 
with alkaline permanganate in the cold, the erythritol CioH2oOi characteristic of y-ter- 
pinene; m. p. 236 to 237°. On boiling with dilute sulphuric acid in a current of steam 
a smell of phenols (thymol, carvacrol) was 'noticed. When several fractions (b. p. 175 
to 179°; 176 to 178°; 177°) were brominated in absolute ethereal solution,^ after being 
chilled down to freezing mixture temperature, separation of a solid, slightly yellow 
bromide was repeatedly observed which, however, on suction or on spreading on 
cooled porous plates decomposed rapidly with liquefaction and evolution of hydrogen 
bromide. Since just these fractions yielded /-terpinene dihydrochloride in good amount 
it might have been the case of a bromide of /-terpinene. Possibly the investigators 
working on terpinene have hitherto overlooked the fact that /-terpinene, in absolute 
ethereal solution at reduced temperature forms a bromide which is unstable at ordinary 
temperature when exposed to the air. That a-terpinene was absent was concluded 
from the non-formation of the nitrosite; likewise we were unsuccessful in obtaining, 
by oxidation with alkaline permanganate, the dihydroxy dimethyladipic acid charac- 
teristic of a-terpinene which in many cases, besides- /-terpinene, is a constituent of 
essential oils. 

Of alcohols, the following were found to be present: — /ina^ooZ, borneol, terpinenol-A^ 
and geraniol. 

The first-named alcohol was found in fraction^ of the b. p. 77 to 78° (6 to 7 mm.) 
and the sp. gr. diso 0.8975 to 0.8991 which were separated from fractions containing 
borneol by sharp fractionating. To judge from the odour, an oil of the b. p. 197 to 
199.5° and the sp. gr. diso 0.8750 consisted of fairly pure linalool from which the 
phenylurethane, m. p. 65°, was obtained without difficulty on treatment with phenyl- 
mcyanate. Oxidation with bichromate mixture yielded citral. 

\-Borneol separated off in the solid state from the fraction b. p. 86 to 102° (8 mm.) 
when distilling in vacuo, and was identified by its odour, its m. p. 204°, and by the 
formation of camphor on treatment with bichromate mixture. 



1) Jahresher. d. Chem. 9 (1856), 616; ace. to Anual. de Chim. Phys. (3) 49 (1857), 148. 






70 Report OF ScHiMMEL S Co. 1922. 

Fractions of the b. p. 86.5 to 91. 5^ and the sp. gr. 0.9403 and 0.9363 showed the 
characteristic smell of terpinenol reminding slightly of terpineol. Since they contained 
additionally a small amount of borneol which could not be removed by freezing-put 
the presence of terpinenol, an alcoholic connected structurally with terpinene and 
therefore often found in oils containing this terpene, had to be proved by oxidizing 
it, by means of cold 1 per cent, permangimate solution, to the glycerol C10H20OS. The 
neutral product obtained hereby (b. p. 160 to 165° [9 mm.]) solidified soon when 
triturated with chloroform and ether. Whereas, however, Wallach^) found the m.. p. 
of the glycerol from terpinenol-4 to be 114 to 116° (glycerol from terpinenol-1 , m. p. 
120 to 121°), the glycerol obtained by us melted already below 1009, thus proving 
that the body was not uniform. Only after repeated fractiional crystallization it was 
possible to isolate small amounts of the body with the m. p. Ill to 113°. When 
heated with dilute hydrochloric acid in a current of steam it yielded, in addition to 
cymene, carvenone; semicarbazone, m-. p. 201 to 202°. The sublimate of the glycerol 
.melted at 128 to 129°. A somewhat larger amount of the glycerol was prepared and 
transformed, by oxidation with alkaline potassium permanganate, into the a,a'-dihydroxy- 
a-methyl-a'-wopropyl adipic acids of the m. p. 205 to 206° and 188 to 189°. Although 
we did not succeed in' separating the resulting mixture of the active and the inactive 
acid (m. p. 195 to 200°) into the separate acids with the correct melting point, it was 
possible to isolate, from the mixture of bilactones obtained by heating the acid mixture 
to 200° (m. p. 65 to 71°), the bilactone, m.,p. 70 to 72°, corresponding to the acid 
m. p. 188 to 189° by resorting to fractional crystallization. This bilactone easily 
passed over, on heating with caustic potash, into the acid m. p. 187 to 188°. 

A further proof for the presence of terpinenol-^ in the fraction mentioned above 
was furnished by the formation of terpinene dihydrochloride, m. p. 51 to 52° when the 
solution in glacial acetic acid was saturated with hydrogen chloride gas. However, 
we were unsuccessful in attempting tb prove the presence in the terpinenol-containing 
fraction of «-terpineoJ, which would account for the unsharp melting point of the glycerol. 
CioHaoOj owing to a possible admixture of the glycerol of a-terpineol (m. p. about 121°). 
It may,^ therefore, be taken for granted ihat the incorrect melting point of the neutral 
oxidation-product maybe ascribed to the low content of borneol in the terpinenol fractions. 

Small amounts olF geraniol were found to be present in fractions boiling between 
91.5 and 102° (7 mm.); di6oQ.9259; faint odour of geraniol. On treatment of the 
solution in benzene with phthalic anhydride and subsequent saponification of the 
resulting solution of the ester-siilt, an oil, b. p. 225 to 231°, with a pronounced oddur 
of geraniol was formed. It yielded a diphenylurethane, m. p. 82°; on oxidation with 
bichromate solution, citral was the result. 

The high-boiling fractions (b. p. 102 to 106° [7 mm.]; diso 0.9326 to 0.9386) were 
not entirely free from thymol. After the phenol had been removed and the liquid 
distilled over sodium, a sub-fraction showed the following properties: — b. p. 259 to^ 
264°; di6o 0.9105; «d+7°54'. On heating with glacial acetic and sulphuric acids, 
followed by steam-distillation, caryophyllene alcohol, m. p. 94 to 95° was formed, so 
that the presence of caryophyllene in the sesquiterpene fraction was rendered probable. 
In addition, small amounts of a second sesquiterpene and possibly also of a sesqui- 
terpene alcohol seemed to be present in this Spanish oil. 

Hence, the following bodies, besides thymol, have been proved to be important 
constituents of the oil in question : — a. new terpene, b. p. 155°, camphene, /-terpinene. 



I) Liebig's Anndlm 360 (1906), 169. 



Commercial AND SCIENTIFIC NOTES ON ESSENTIAL OILS. 71 

Z^borneol, liilalool, and terpinenoI-4; amyl alcohol, amyl carbinols, y^, ^'-hexenol (?), 
/?-pinene, i?-cyhiene, geraniol, and caryophyllene are likewise present. Hitherto, the 
following constituents of Spanish thyme oil (however, of different botanical origin) 
had been found : — a-pinene, j>-cymene, bomeoJ, and linalool. 

From the dry herb of Thymus vidgaris, L'., , collected in July near Terracina, pro- 
vince of Rome, P. Leone and E. Angelescu^) obtained by steam-distillation 1.06 per cent, 
of a dark red oil with a strong aromatic odour and the following constants: — 
d^ 0.9250, 0280 — 2.40° (taken in white electric light), nujao 1.4964^, a. v. 3.5, sap. v. 
14.9; ester v. 11.4, corresponding to 4 per cent, linalyl acetate. Steam-distillation 
being repeated, the constants of the lemon-yellow oil were: — d^ 0.9194, Mdm© — 3.57°, 
Hdmo 1.49505. 

The phenol {thymol, m. p. of the nitroso derivative 141 to 142°) was removed by 
shaking with 5 per cent, caustic soda solution. Thymol estimated, 38 per cent, according 
to the iodine method of Kremers and ' Schreiner. The non-phenolic part of the oil 
showed, after acetylation, the sap. v. 112, corresponding to 30.8, and 14.1 per cent, 
when calculated on the entire oil. After repeated fractional distillation under ordinary 
pressure the following fractions were obtained:— 1. up to 165° (1.3 per cent); 2. 165 to 
175°(23.1 per cent); 3. 175 to 185° (30.8 percent); 4. 185 to 195°(6.5 percent); 5. 195 to 
205° (5.5 per cent); 6. 205 to 225° (4.8 per cent.); 7. 225 to 235° (10.6»per cent). 
After boiling fractions 2 and 3 for five hours with sodium, the authors succeeded in 
obtaining 13 per cent (calculated on the entire oil) of a fraction boiling at 171 to 176° 
which consisted nearly entirely of cymene (hydroxyisopropyl benzoic acid, m. p. 156 to 
157°). The free alcohol seemed to be a mixture of borneol and linalool, which the 
authors, however, were unable to identify. ' 

From a drug which in its morphological and anatomic characters coincided 
Completely with Thymus vulgaris, L R. Kofler*) obtained an oil which differed largely 
from thyme oil owing to, a content of cineole and containing but very little, if any, of 
thymol. The author takes this fact for a further proof for the extraordinary variability 
of the species of the genus Thymus also in their chemical behaviour ^). 

Turpentine Oil. — There are in the main three species of Pinus used in the 
United States for the production of turpentine; viz., Pinus palustris, Mill., which 
supplies the largest quantity by far, Finv^ heterophyUa (Ell.), Sudw., and Pimis echinata. 
Mill. The Bulletin No. 898 (1920) of the U. S. Dep. of Agriculture*), which contains much 
useful information on the turpentine industry of country, names in addition to Pinus 
palustris and Pinus caribcea (heterophylla) B\sd Pinus ponderosa, Dougl., (Western yellow 
pine)*) as being tapped for turpentine. According to this bulletin, about 75 per cent of 
the world's supply of turpentine is produced in the United States, the relative production 
in the various States being about as follows: — Florida, 37 per cent; Georgia 19 per cent.; 
Louisiana, 15 per cent.; Alabama, 12 per cent.; Mississippi, 9 per cent; Texas, 7 per cent; 
North and South Carolina, less than 1 per cent Formerly North Carolina produced the 
bulk of the world's supply of turpentine, but now its pine forests are almost exhausted. 



») Gazz. chim. ital. 51 (1921), II. 391. — •) Pharm. Monatsh. 1921, N* 3. Ace. to Pharm. Ztg. «6 (1921), 484. 
— *) Dorronsoro found likewise in Spanish thyme oils originating from Th. Mastichinaf L. and Th. cephalottis, L. up 
to 60 per cent, of cineole by the resorcinol method. Compare also p. 65 of the present Beport. — *) Joum. 
Soc. chem. Ind. 40 (1921), R. 165. — . *) Comp. also Beport April 1913, 101. According to Engelmann^ a botanist 
who died in St. Louis (Missouri) in 1884, JVwms ponderosa is the .most widely spread pine of the West in 
California and Oregon, thriving on low and high mountains, even also in the plain, on sandy-gravelly soil. 
Beissner, Handhuch der Naddholzkunde, 2"*' edition, p. 387. 



72 Report of Schimmel § Co. 1922. 

The distilling plant is simple and has not been improved materially during the 
last 50 to 60 years; it consits of a copper still of 500 to 1000 gallons capacity, with 
a still-head connected to a targe copper condensing-coil cooled in water. From 7 to 
14 barrels of oleo-resin go to make a charge, depending on the nature of th^ oleo- 
resin and the size of the still. This i^. heated over an open fire. >yhen most of the 
water originally present in the oleo-resin has passed over, as shown by the peculiar 
sound which is heard close to the tail-pipe of the condenser coil, a small stream of 
water is admitted to the still. The yield of oil varies from 16 to 22 per cent. It is 
mostly shipped in wooden barrels, treated internally with two coats^ of glue and holding 
50 to 53 gallons. In the more western States the larger producers employ tank-cars 
of 5 to 16 thousand gallons capacity. On arrival at the primary markets each barrel 
or tank-car is inspected as to quality and volume. 

The total production in the U.S.A. for the 1919 season amounted to 366000 casks 
(50 galls.) of turpentine oil and 1237000 barrels (500 lbs.) of rosin; during 1920 up to 
August 1**, 237155 casks of turpentine oil and 712387 barrels of rosin were produced, 
the estimated production for the rest of the season being 233876 casks of turpentine 
oil and 739679 barrels of rosin. # 

At present a little less than 10 per cent, of the total is wood turpentine obtained 
from stun^ps and dead or fallen timber by steam or destructive distillation; this source 
erf turpentine is becoming more important. 

As per a statistics of the Turpentine and Rosin Producers' Association*) the U.S.A. 
supplied before the war about 85 per cent, of the world's requirements of naval stores. 
At present, the percentage is only 62, the remaining 38 per cent, being contributed by 
France, Mexico, British India, Spain, Italy and other countries. Especially France has 
increased her production during the last four years. In 1920/21 it amounted to 
250000 barrels (50 gals.) of turpentine oil and 875000 barrels of rosin. Spain supplied 
twice* the quantity of previous years; viz.^ 41000 casks of turpentine oil. The exports 
of the U.S.A. in 1921 amounted to 73125 casks of oil and 508334 barrels of rosin 
(500 lbs.), as compared with an average of 359375 casks of oil and 1354068 barrels 
of rosin in the last ten years before 1914. 

In Central and West Durango (Mexico), there are about 15000000 acres of pine 
forests, the larger part of which is owned be the Federal Government. As the material 
is fit for the production of turpentine, an American cornpany erected there a modern 
distilling plant. The trees can be tapped for three to four years running. Each trunk 
yields during one season more than one quart of pure, white turpentine oil and 6 lbs. 
of rosin, the quality of which is not inferior to the products of other countries*). 

Spain's turpentine industry') is in the hands of the Union Besinera Espanola, one 
of the largest and most powerful trusts of the country. This company's report (1919) 
contains the following figures: — 

Production Rosin Turpentine oil 

1915 . . . . 15054.593 tons 4331.429 tons 

1916 .... 16238.545 „ 4868.871 „ 

1917 . . . . 14364.773 „ 4599.066 „ 

1918 .... 13918.298 „ 4101.384 „ 
1919 .... 11397.619 „ 3647.656 „ 

») Drug and Chem. Markets 10 (1922), 155. — «) Drug and Chem. Markets 9 (1921), 1038. — «) Oil, 
Paint and Drug Reporter 100 (1921), No. 21, p, 32. . . 



Commercial and scientific notes on essential oils. 73 



Sales 


Rosin 


Turpentine oil^ 


1915 . . , 


. . 15153.998 tons 


45P4.281 tons 


1916 . . 


. . 14273.563 „ 


5670.763 „ 


1917 . . 


. . 17269.470 „ 


4414.491 „ 


1918 . . 


. . 9321.734 „ 


4198.808 „ 


1919 . . 


; . 14257.651 „ 


4408.^47 „ 



Spain's exports of turpentine oil, rosin and tar were as follows: — 

in first 4 months 
1919 1920 1921 

Terpentine oil . . 4591.216 tons 3081.873 tons 518.495 tons 
Tar. .... . 13041.131 „ 12181.345 „ 1039.588, „ 

Rosin 809.243 „ 544.484 „ 36.159' „ 

Portugal produced*): — 

Year Rosin Turpentine oil 



1916/17 
1917/18 
1918/19 
1919/20 
1920/21 



3000 tons 950 tons 

4000 „ 4200 (?) „ 

6000 „ 2000 

6300 „ 1800 

12400 „ 3600 



n 
n 



It is reported that there are no stocks of turpentine pil, whereas those of rosin 
are estimated at about 10000 tons. Portugal's home consumption is 2000 tons each 
of turpentine oil and rosin, annually. The pine forests of Portugal (773000 hectares) 
cover about the same area as those of south-western France (200000 hectares in the 
Gironde, 500000 hectares in the Landes and 50000 hectares in the Lot-et-Garonne). 

According to Th. M. Ainscough ^) the Indian production of rosin and oil of turpentine 
becomes more and more important. It started on a small scale about 25 years ago 
and, owing to the activity and the skill of the foresters, who were well acquainted 
with the methods employed in the "Landes" of France (gemmage a vie and gemmage 
a mort)^ developed first in the United Provinces of India and later on in the Panjab 
to its present state. In 1919 an area of 97525 acres of pine forest (in the main Pinus 
longifolia, Roxb.) yielded 4615 tons of olep-resin, from which 2400 tons of rosin and 
more than 156000 gallons of turpentine oil were prepared*). 

F. Henrich®) reports on an investigation of pine balsams (Pinm sUvestris, L), carried 
out conjointly with A. Pfotenhauer and under the assistance of F. Pensel. Generally 
speaking the samples, which came from the neighbourhood of Erlangen and had been 
collected in different months of 1917 and 1918, had the same composition : — d^O.8560, 
0.8573, Mdwo + I^.I, +13.60; acid v. 0.61, 0.40; ester v. 1.67, 1.58; sap. v. 1.73, 1.62«). 
The resinous residue of one balsam, collected in August from trees growing on fatter 
soil, contained even less esters than that of the other balsams. About 22 to 25 per cent 
of the balsam were volatile with steam''). The turpentine oil whose angle of rotation 
did not exceed [a] +28.41°, consisted of a small quantity of /^-pinene (nopinic acid. 



1) Oil, Paint and Drug BepoHer 100 (1921), No. 21 , p. 32. — «) Ihidem 101 (1922), No. 1 , p. 32. — ») Comp. 
Gildemeister and Hoffmann, The Volatile Oils, 2"*' edition, vol. II, p. 69. — *) Comp. also Berichte (German) 
1920, 132; 1021, 48. — ») Zeitschr.f. angew. Chem. 84 (1921), 363. — •) There seems to be a printer's error, 
for tfie sum of the acid and ester values must equal the saponification value. — ') Comp. Beport 1916, 54. 



<^-^il 



7*: 









■jKiVt.; 



t-V*. 






e^.'i- z ■'- 






fe: 



\ 



Report of Schimmel S Co. 1922. 



m. p. 126°) and apparently a mixture of d-* and Z-a-pinene, in which the c?-a-compound 
predominated (nitrosochlorid^ 103°). \ 

The authors found too that the unsaponified fraction of the crude oil of turpentine 
had a somewhat higher specific gravity than the saponified fractions, but that the 
optical rotation was not considerably influenced by the saponification. It was impossible 
to establish what the components of the saponified products were. 

One sample of turpentine oil (d^ 0.8624; [«]d»o + 17,13o C = 87.0 per cent, j 
H = 11.12 per .cent) was exposed to the air and examined from month to month. 



After six months the constants were: — d^ 1.0584, [ttlD»o + 1.44°, C = 71.03 per cent., 
H = 9.45 per cent In another sample of purified turpentine oil from pine balsam, 
which had been kept for three years in an Erlenmeyer flask, the presence of small 
quantities of a peroxide, of acid-like components (not abietinic acid) dnd of 20 per cent 
of resene was proved. (Tschirch found in a six months old, autoxidized French 
turpentine oil above all a resene-like body in addition to a small amount of resinolic 
acid. Arch. d. Pharm. 2138 (1900), 645.) Besides, the authors obtained from this sample 
a small quantity of a dextrorotatory oil, smelling like menthol, but which it was 
impossible to examine any further. 

M. Vezes^) thinks it possible to determine the proportion of «-pinene and /?-pinene 
(nopinene) in French turpentine oil with the aid of Darmois'*) polarimetric method. 
The proceedinjg, which it would lead us to far to describe in detail, consists in that 
the rotatory power of 5 fractions of equal size is' determined for three colours. With 
the aid of the known rotatory power of «- and A-pinene the proportion of the quantities 
of these terpenes can easily be calculated. V^zes found in thiis way that a French oil 
of turpentine (b. p. 154 to 162° under ordinary pressure, without the less volatile' hydro- 
carbons) contained 80.9 per cent of a-pinene. It may be added that the author himself 
thinks the method has not been sufficiently verified yet and that he calls the values 
found only approximately correct 

F. C. Palazzo, Mina Palazzo and E. Azzarello have published conjointly a series of' 
articles^) on investigations of Italian turpentine oil, the results of which have been 
discussed in part in our previous Reports*) (on oil of turpentine of Pimts Pinea, L, 
and of Pimis Pinaster, Sol.). 

One of these articles (no. II! by F. C. Palazzo and E. Azzarello) deals with the 
applicability of Italian oil of turpentine. As has been shown before, the oil obtained 
in Tuscany^) (b. p. 170 to 1729, diso 0.852, nD»o 1.474, inflammation point 50°) consists 
chiefly of Mimonene and differs considerably from the products of other countries, 
which contain a-pinene above all. It is pointed out in the article, why just these 
properties (lesser volatility, better capacity for dissolving resins, balsams, fats and 
waxes, elevated inflammation poiht, §c.) make the Italian turpentine oils very fit and 
valuable for certain technical purposes, such as the manufacture of varnishes, oil 
paints, §c. It is further mentioned that the vapours of these oils, contrary to the 
products containing pinene, do not injure the human organism. 

Pinus halepensis, Mill., the turpentine of which might likewise be put to use, also 
occurs in Italy. M. Palazzo^) investigated oils of turpentine, obtained from Knus 
kalepensis in Cecina and Vada. The yield in turpentine which was obtained according 



1) Compt. rend. 172 (1921), 977. — «) These, Paris 1911, p. 53. — ») U trementine italiane. Nota I, IJ, 
IH, IV. From Annali del JR. Istituto Superiore Forestale Nazionale, vol. II, 1917 and vol. IV, 1919. As per a 
reprint kindly aent us. — *) Comp. RepoH 1917, 72; 1918, 50. — ») The turpentine of the different PinuB 
species, among which Pinus Pinea preponderates, are not distilled separately. 



Commercial and scientific notes on essential oils. 75 

to the mbthod used in the Landes^) in the course -of about five months, was 
approximately 1«3 kilos per tree. If the normal time of seven to eight months was 
allowed, Palazzo thinks that the output -could be increased to 1.8 kilos per tree. 

The product yielded on an average about 20 per cent, of turpentine oil with the 
following properties: — diBo 0.8635, [«]di5o + 46.710, rfoigo 1.4688, soluble in 7 parts of 
90 per cent, alcohol, inflammation point 32 to 33°. Wheri subjected -to fractionated 
distillation, the six first fractions (90.4 percent.) passed over between 154 and 158° 
and consisted almost exclusively of <^pinene. The 7*h and 8*^ fractions boiled from 
158 to 160° and from 160 to 163°, respectively. 

The methods for detecting and estimating toluene, xylene, solvent naphtha and 
other coal-tar derivatives in turpentine oil, as suggested by Marcusson ®> ^nd Krieg^r^) 
have not been found reliable by V. E. Grotlisch and W. C Smith*) especially if small 
quantities are concerned. Grotlisch and Smith have therefore contrived a new method, 
according to which the turpentine oil is first treated with dry hydrogen chloride. The 
pinene hydrochloride formed , is' separated from the other liquid, which is then distilled 
under reduced pressure The unchanged coal-tar oils pass over with the first part of 
the distillate. This is sulfonated with fuming sulphuric acid and distilled with ste!am. 
In the case of pur^e oil of turpentine, a very small quantity of a dark yellow volatile 
oil of disagreeable smell is obtained : — index of refraction iidmo slightly above 1.500. 
If any mineral oil is present, an almost Colourless product is obtained, having the 
characteristic mineral oil odour and an index of refraction below 1.500, generally below 
1.4800. If coal-tar derivittives were present, they can be recovered as such to the 
extent of 45 per cent. The quantity present thereof is found therefore by multiplying 
the result of the analysis with 2.2. —The sulphuric acid used must always have the 
same concentration and contain 3 to 4 per cent, of free SOs. Otherwise the results 
do not agree. This method is not strictly applicable to wood turpentine oil, unless 
the adulteration exceeds 4 per cent., as small quantities of benzene hydrocarbons occur 
as normal components of this oil. f 

With reference to Salvaterra*s arttcle "On New Methods of Investigating Turpentine 
Oil", in which the author declares that Herzfeld and Marcusson's method is not aftogether 
free from objection*), J. Marcusson*) points out once more the usefulness of his nitric 
acid test for the determination of light petroleum in turpentine oil. According to these 
explanations Marcusson's investigations of mixtures of light petroleum and turpentine 
oil would prove that his method suffices completely for technical purposes. The nitric 
acid method is applicable not only for turpentine oils, but also for pine oil and pinolene 
and does not depend upon what sort of light petroleum is present. Even small quantities, 
such as 2 to 3 per cent, of light petroleum, were still to be detected with his method. 

H. Heller') publishes an extract of H. Salvaterra's article on the investigation of 
turpentine oils®) discussed by us already, under the title of "Mew Methods for the 
Investigation of Turpentine Oils". 

As C. M. Sherwood^) reports, the extraction of rosin, pine oil and turpentine 
from dead pine wood was begun in 1909 by the Yaryan Naval Stores Co. at Gulf port 
and Brunswick, Ga., Since 1921 this company works conjointly with the Hercules 



1) Omimage U vie or gemmage a mart; comp. Gildemeister and Hoffmann, The Volatile Oils, 2"«' edition, 
vol. H, p. 69. — «) Chem.Ztg. mi\9\2), 4S\. — ») J6tVi. 40 (1016), 972. — ^) Joum.'ind. nnd Eng. Chem. IS 
(1921), 792. — ») Cf. Sericht {Germ&n) 19^1, 49. — •) Chem. Ztg. 46(1921), 418. — ») Deutsche Parf.-Ztg. 7 
(1921), 131. — «) Cf. Bericht (German)^ 1921, 48. - ») Chem. and Met. Engin. 26 (1921), 994. 



76 Report of Schimmel S Co. 1922, 

Powder Co.^) The combined maximum worked per day is about 1000 tons of wood. As 
Sherwood declares, it cannot be said that this industry has been profitable up to the 
present time, but it may nevertheless be called upon to act an important part in future 
in the production of naval stores. The wood chiefly used is the Southern long-leaf 
pine (Pimts jpcdustris) . The material may be divided in stump wood and top wood, the 
former being richer in extractable products. H seerns to be generally true that the. 
twisted grain wood is richer than the straight grain. The distribution in the roots is 
also interesting. The lateral roots are very rich in rosin, turpentine and pine oil; the 
tap root is soft and spongy and contains practically no valuable products. Good land 
yields 8 to 15 tons of wood per acre, depending on the section of the country. The 
milled wooc( is steamed for 3 to 4 hours in ar^ extractor, when all the easily boiling 
constituents (called turpentine by the author) and about half of the less volatile ones 
(pine oil) are distilled off. This distillate, consisting of approximately 70 per cent, of 
light and 30 per cent, of heavy wood turpentine oil is then fractionated. The steamed 
wood is boiled with a solvent, generally gasoline, in order to obtain the rosin and the 
heavy oil still left behind. The solvent and the heavy oil extracted are separated from 
the rosin by repeated distillation. 

The light wood turpentine oil obtaihed that way distinguishes itself by its uni- 
formity and has the following constants: — Initial b. p. 154 o, constituents boiling belOw 
ITQo = 90.5 per cent., residue 1 per cent, df|| 0.865, no 15.50 1.469, flash point (Abel, 
closed Cup) 340. This wood turpentine oil has not tHe fragrant, sweet odour of freshly 
distilled gum turpentine oil. 

A high-grade commercial pine oil manufactured at Brunswick, Ga., had the following 
properties: — boiling range 180 to 225°, di6.5o 0.935, nDis.so 1.479, residue 3 per cent., 
colour light istraw. According to Sherwood, the composition of pine oil, which resembles 
turpentine oil very closely, is rather uncertain. We would mention therefore that, years 
ago*) we thoroughly investigated a yellow pine oil, i. e., a wood turpentine oil obtained 
from the stumps, most likely from Pinm palustris, and found the following constituents: 
^a-terpineoI, «- and /^-pinene, camphene, Mimonene, dipentene, /-terpinene, cineole, 
i-fenchylalcohol, campher, Z-borneol and methyl chavicol. 

Pine oil when first produced was considered practically worthless. In later years, 

« 

however, it has become valuable in many ways, e.g. in the flotation process, as basis 
of a variety of medicinal and desinfectant solutions and as a solvent in the rubber, 
paint and varnish industries. 

The rosin obtained through the extraction is generally ruby red and consists, like 
ordinary rosin, chiefly of abietic acid, CaoHsoOa^). The percentage found by analysis 
were C 78*12, H 9.90 and O 11.98 per cent. Wood rosin is said to have an advantage 
over gum rosin because of its uniformity and cleanliness. 

Also in Germany stumps are used again on a larger scale for the production of 
turpentine oil. As F. O. Koch*) reports, the following yields were obtained from resinous 
stumps (root wood of Finus sUvestns, L.) according to Franz Schmidt's method: 5 per cent, 
oil of turpentine, 1 per cent, acetone, 8 per cent, tar and 22 per cent, charcoal. Koch 
then makes some remarks concerning the problem of the production of turpentine 
and pine oils from stump wood, remarks which are not altogether reliable and invite 



*) In 1910 there were 30 plants in the U. S. A., where yellow pine was distilled, in addition to smaller 
quantities of Norway pine and Douglas fir. Cf. Gilderaeister and Hoffmann, The Volatile Oils, 2"«* edition, 
vol. II, p. 98. — «) RepoH April 1910, 103. — ') The acid CjoHgoOj is pimaric acid. — ,*) Chem. Ztg. 45 
(1921), 699. 



Commercial AND scientific notes on essential oils. 77 

criticism. Link^) has already found the proper answer, so that we may refrain from 
going into details. We would only add that the good quality of the French product 
is due to the peculiar composition of the French turpentine^ and to the methods of 
producing the gum and distilling the oil. Koch's assertion "that an excess of volatile 
constituents in the gum, the loss of whjch during the exudation has no great effect" 
was responsible for the superiority of the French turpentine oil, is absolutely unfounded. 
As to the author's opinion that the dire(ft production of turpentine oil from stumps 
had so far been unknown in Germany and other countries, Link remarks that about 
40 years ago already an excellent pure turpentine oir has been obtained by steaming 
resinous wood. Link mentions that he himself constructed a factory in Western 
Prussia, in 1893, and another in Volhynia, in 1901, where the oil was drawn from 
the wood in a specially constructed apparatus, before being carbonized. The high 
costs of production, combined with the competition from abroad, which sent the prices 
down, prevented the construction of more such plants. He thinks that now conditions 
have altered somewhat, as more trees are cut in the forests and the competition of 
other countries is less keenly felt. 

The factory jn Volhynia, erected by Link, produced in the first four years 1554 tons 
of turpentine oil, 144.48 tons of pine oil, 10298.4 tpns of tar, 1680 tons of Acetate of 
lime (80 to 82 per cent), 210 tons of wood-spirit (calculated as 1(X) per cent.) and 
12196.8 tons of charcoal, from 168000 cubic metres of wood. 

The products offered as turpentine oil in Esthonia during the last three years were, 
according to J. Schrndelmeiser®), exclusively pine or sulphate oils. The pine oil pro- 
ducedMn Esthonia contained from 50 to 75 percent, of pinene; that from the East was 
also rich in pinene, whereas the Finnish product, contained more cymene. If, like in 
Finland, the oil is obtained at a higher temperature, cymene forms at the expense of 
the pinene. The Esthonian crude oil differed greatly in that sometimes up to 75 per cent, 
could be distilled off with steam, but in some cases barely 20 per cent. The sulphate 
Oil, coming from the Swedish wood piulp factories, but bought and sold as French oil, 
consisted almost entirely of cymene. 

the odour of sulphate turpentine oil can be improved according to L. Schmidt^) 
by heating the oil for two hours with sodium peroxide under a reflux condenser. The 
product is then filtered in order to separate it from the yellow deposit formed and 
distilled with steam. The turpentine oil thus obtained is said to resemble the French oil. 

F. Baum, of Jena University's Women's Hospital, usied against certain inflammations 
injections of the following kind: turpentine oil 4 grams, eucupin 0.2 grams, olive oil 
16 grams. As albuminuria was sometimes noticed after this treatment, one must be 
careful in case of inflammation of the kidneys^). 

As a treatment ot spotted fever, A. Brenner*^) recommends oil of turpentine (to be 
taken every hour in doses of 0.05 to 0.1 gram) or terpin hydrate. Besides, the remedy 
is to be inhaled. 

Valerian Oil. — In Belgium, the costs of the production of valerian root, including 
farmt-rent, wages, Sc, are four times as high as before the war. The 1920 crop is 
said to be of very good quality, the roots being clean, heavy, of light colour and 



1) Ch&m. Zig. 45 (1921), 820. — 2) Pharmacia 1»21, No. 3, p. 16. — ») D. R. P. 340126, dated 27. II. 1919. 
As per Chem. ZentralM. 1921, IV. 1016. — *) Med. Klinik 1921, No. 13. As per Vierteljahresschr. f. prakt. Phami. 
18 (1921), 130. — •) Miinch. tned. Woehenschr. 1921,. p. 992. As per Therap. Halbmonatsh. 35 (1921), 642. 



78 Report of Schimmel & Co. 1922. 

likely to keep in. good condition for several years. As the cultivation of valerl^ Is ' 
no longer profitable enough, the Belgian farmers mean to continue it only, if better 
prices can be obtained'). 

Indian Valerian OH. — Valerian root from the western spurs of the Himalayas 
contains an essential oil, of which a sample was sent us recently. It behaved as 
follows; — d«,= 0.9361, hq— 3406', nD»o 1.48712, acid v. 37.3, ester v. 39.8, ester v. , 
after acetylation 69.1, soluble in 0.3 vols, and more of 90 per cent, alcohol, whereas 
of 80 per cent, alcohol even 10 vols, did not suffice for dissolving the pil. The colour 
was yellowish green, the odour strong and lasting. 

We were told that It came from Yakriana Wailichii, DC. 

Vetlver Olt. — We stated quite a new kind of adulteration/ in a Reunion distillate, 
received some time ago. Among other substances, it contained glycerin acetate, an 
admixture which we had not expected at first. The oil was conspicuous by its. 
properties:— d,so0.9,911. »i,H6O20', no„o 1.51862, acid v. 0.5, ester v. 43.5, not yet 
soluble in 10 vols, of SO per cent, alcohol. Comparing these figures with those for 
normal Reunion vetiver oils Jdua 0.990 to 1.020; % +22 to +37"; ncno 1.515 to 1.527; 
acid V. 4.5 to 17; ester v. 5 to 20; soluble in 1 to 2 vols, of 80 per cent, alcohol), 
one sees at once that oil deviates the polarized light far too little, has too low an 
acid value and too high an ester number, whereas the solubility is absolutely in- . 
sufficient. As these properties do not tally either with those of vetiver oils from 
other sources (Fiji islands, Seychelles), there was sufficient cause for suspecting 
adulteration. Although we could not say anything definite straight off, we had to 
refuse the pil. The supplier, most likely in France (we bought the article from a 
middleman) was very indignant in consequence, but soon assumed a different tone, 
when we let him know that we had meanwhile succeeded in proving the presence of . 
glycerin acetate in the oil. The following observation had shown us the way. The 
part of the oil which was insoluble in 80 per cent alcohol and the soluble part, after 
having'been separated off on adding water to the solution, were both lighter than the 
original oil. It was therefore evident that the alcohol had also taken up a heavier 
component which, as water did not separate it off, had to be soluble in water. It 
was therefore natural to think of glycerin, acetate, the presence of which could be 
proved on closer investigation. It was recognized by its specific gravity (dito 1.1654) 
and the high saponification value (671.6). The quantity was 5 per cent. 

Tio doubt there was still another adulterant present, for the exceedingly low 
rotatory power and the insufficient solubility are not fully explained by the above 
remarks. Cedarwood oil probably had something to do with it, but we had no cause 
for further investigation, as the oil was taken back. 

Oil of the roots of Viola odorata.— Oneof the oils formed by the decomposition 
of a glucoside is, according to A. Goris and Ch. Vischniac*), the oil contained in the 
roots of the sweet violet, which was discovered quite by chance. At a place where 
violets {Viola odorala, L) grew abundantly, the authors noticed quite a strong violet 
smell, although the plants had no flowers as yet. On closer investigation, it resulted 
that the somewhat herbaceous and impure violet odour emanated from the fresh roots, 
when rubbed. Fowl had scratched there, had thus laid the roots bare and damaged 
them, which caused them to smell. In order to study the matter further, the authors 

') Vliaaiit and Dnggist M (I92i), 404. — ') BuU. Ruiir^-Bertrniia Fits, April 1921, 3. 



Commercial and scientific notes on essential oils. 79 

sterilized 122 kilos of roots, collected near Grasse in March, and extracted them 
thoroughly with hot alcohol, to which some calcium carbonate had been added. The 
product was extracted with hot, aqueous acetic ester and the resulting green extract 
treated with hot water. The watery solution contained the gtucoside and part of the 
already free oil, which was separated with the aid of ether. When some powdered 
ytolet root, which had previously been washed with alcohol and ether, was added to 
the aqueous liquid, a slight alteration of the rotation and the presence of a small 
amount of essential oil was to be noticed^). 

Only a very few data are given about the oil itself. The yellowj aromatic product 
was partly soluble in light petroleum. This component proved to be a cristalline 
mass, which, after having bpen dissolved in an aqueojis solution of sodium carbonate, 
could be precipitated with hydrochloric acid. On treatment with ether, a cristalline 
mass was then obtained which gave a green colour reaction with ferric chloride solution. 

From the part that did not dissolve in light petroleum, a small quantity of salicylic 
acid was obtained after saponification with alcoholic potash lye. The authors take it 
that methyf salicylate was probably present in the roots, as Desmouliere*) arrived at 
the same result, years ago, with Viola tricolor. 

on of Vitex irifolia. — On distilling the leaves and twigs of Vitex trifolia, L. 
" (Viiex ovata, Mak. [?] [Thunb.]), a verbenacea grown in the Ogasawara Islands and 
Kanagawa Prefecture (Jap. h(imago\ Y. Shinosaki*) obtained 0.11 to 0.28 per cent, of 
an oil having a brown colour and a characteristic odour^). Three samples of the oil 
had the fpllowing characters: — diso 0.8908 to 0.9141; odsoct — 39^6' to —47^20'; 
Hdwo 1.4707 to 1.5010; acid v. to 1.75; sap. v. 23.38 to 38.70; sap. v. after acet. 40.14 
to 53.34. The chief constituents of the oil were Z,a-pinene, which gave no solid 
nitrosochloride, camphene (together with pinene:~55 per cent.), terpinyl acetate 
(10 per cent, b. p. 84 to 86° at 15 mm.; dis© 0.9629; no^o 1.4670); a diterpene alcohol 
C20H82O or CgoHsiO (20 per cent., b. p. 165 to 167° at 4 itim.; d^^o 0.9760; aowo — 46° 39'; 
nD2oo 1.5143; sap. v. after acet 42.02). The oil was separated into its three chief con- 
stituents by fractional distillation; the middle part might be suitable for perfumery 
purposes, as it is mainly composed of terpinyl acetate. 

M ♦ 

• • \ 

Oil of Water-hemlock. — A trial distillation of faded roots of water-hemlock 

' {Cicuta virosaj L.) gave us an opportunity of determining some properties of this oil, 

which is but little known. It was yellow and had a faint odour, which it is difficult 

to describe. A similarity with water-fennel and celery, noticed by others on a 

' previous occasion*), could not be stated this time. The following constants were 

• determined: — di6o 0.8909, a^ + \e<^32\ nDMO 1.48480, acid v. 3.7, ester v. 17.7, soluble 

in about 4 volumes of 90 per cent alcohol, but with turbidity which, on standing, 

led to the separation of flakes (paraffin?). The yield amounted to 0.04 per cent 

Worntwood Oil. — F. Rabak^) publishes the following observations wade with 
wormwood, Artemisia absinthium, L, under cultivation at the Arlington Experimental 
Farm, Arlington, Virginia, for a period of years. During that time the plant was 



^) These facts indicate the presence of a glucoside, it is true, but the authors themselves have to admit 
that it has not been proved as yet. — *) Ct Beport April 1904, 88. — «) Jbum. cAem.Jnd., Jajpon 24 (1921), 
191. Joum. Soc. chem. Ind. 40 (1921), A. 411. — *) Years ago, a sample of the essential oil of Vitex trifolia, L. 
has been distilled from a specimen growing in the Botanical Garden of Sumatra, which contained cineole. Comp. 
Gildemeister and Hoffmann, The Volatile OilSf 2"'' ed., vol. Ill, p. 409. — *) Cf. Gilderaeister and Hoffmann 
The Volatile Oils, 2r^ edition, vol. Ill, p. 326. — «) Joum. industr. and engin. Chem. 18 (1921), 536. 



SiW^-' 









m--^' 



'■■r: 









80 Report of Schimmel § Co. 1922. 

distilled both in the fresh flowering and in the dry condition, and also at different 
stages of growth. A number of the oils obtained were subsequently examined in the 
laboratory and compared from the standpoint of their physical and chemical properties. 
The conditions of distillation in every instance were identical. The yields of oil from 
the fr^sh flowering herb varied with the climatic conditions from year to year, oscillating 
in the period from 1907 to 1919 between 0.12 and 0.24 per cent. The greater the 
number of clear and partly cloudy days, the greater was the tenden9y of the plant 
to high yields of oil, whereas high rainfall and low temperature apparently tended 
toward low content of oil. The Oils distilled from the dry plants were uniformly darker 
in colour and stronger in odour. They >had a higher ester content (thujyl acetate 35 
and 27.3 per cent.) than the ordinary oil (thujyl acetate 32.2 and 24.1 per cent.). It 
seems therefore that drying favours the formation of ester ^). The maximum yield of 
oil was attained during the budding and flowering period. There was a decided 
decrease in the fruiting stage of the plant (in 1910: — from 0.20 to 0.08 per cent). 
The content of free acids (as acetic) and of thujyl alcohol decreased as the plant 
passed from the budding to the fruiting stage. 

Wintergreen Oil. — We would briefly mention two wintergreen oils received 
from Java (doubtless from Gaultheria punctata, Blume), as such distillates are found 
in commerce from time to time. They were colourless and behaved, as regards odour 
and constants, very much like the Indian' oil of the same botanical origin, described 
by us some time ago*): — digo 1.1 873 and 1.1861, ccd+O'^. nojoo 1.53639, acid v. 5.4 
and 4.8, ester v. 364.9 (= 99 per cent, of methyl salicylate) and 356.6 (= 96.8 jper cent, of 
methyl salicylate), soluble in 7 and 8 volumes, respectively, or more of 70 per cent, alcohol. 

These oils differ from the American distillate of Gaultheria procumbens, L, in that 
they are optically inactive; besides, their arotna is not so fine. 

Indian Wintergreen oU. — According to Puran Singh ^), the fresh leaves of Gaul- 
theria f ragrantissima, WaW.f collefjted in Assam during the winter, gave as much as 
0.65 per cent' of oil^ or 1.2 per cent calculated on dry material. The Nilgiri plant 
gave only 0.12 per cent of oil from fresh leaves. The plant grows gregariously in 
the Nilgiris, in Assam and Ceylon, but for a regular supply of the leaves it would be 
ftecessary to cultivate it on an extensive scale. 

Wortnsieed Oil. — The demand seems to increase in the Dutch Indies too. As 
the Dutch Chamber of Commerce in New York*) communicates, considerably larger 
quantities of wormseed oil were produced in 1920, mostly in plantations connected 
with the cultivations of the Government. Nevertheless the home production was not 
large enough to satisfy the demand. 

As so much attention has recently been paid to the East Indian wormseed oiP), 
a sample originating from Java was very welcome, as it gave us ah opportunity of 
getting acquainted with that product The following constants were observed, diso 0.9662, 
ai> + 0°4', nDjoo 1.47867, acid v. 0.9, ester v. 9:8, soluble in 5.8 vols, and more of 
70 per cent, alcohol, there being a slight turbidity in the beginning. The odour differed 
somewhat from that of the American oil, the smell of ascaridole being less strong. 



^) It must be taken into consideration, however, that the volatile constituents escape during the drying 
process. — ^) BepoH October 1911, 97. — ") Perfum. Record 12 (1921), 51. — *) Holland and her Colonies 
1 (1921), No. 7, page 15. — ») Comp. Berichte (German) 1920, 59; 1921, 15. 



Commercial and scientific notes on essential oils. 81 

Our friends say that in Java only tlie seeds are distilled. The oil obtained in a 
comparatively small quantity is not exported but consumed in the country. It is con- 
sidered inferior to the American product, as it is said to contain less ascaridole. The 
wormwood cultivation in Java is rather difficult, as the seeds do not ripen at the same 
time. The plant itself remains low and herbaceous. Plantations on a large scale have 
been abandoned, as it was recognized that it would be impossible to compete with 
the United States under normal conditions. 

Chenapodium herb OiZ.— As is known, the American wormseed oil is distilled from 
the seeding, plant of Chenopodium amhrosioides, L., var. anthdminticum, Gray. We had 
an opportunity of late to distil the herb by itself and shall here report on our experience. 

Fresh chenopodium herb, without seeds, yielded 0.0057 per cent, of an olive-green 
oil showing the following constants, diso 0.8552, «d + 1° noaoo 1.48141, acid v. 2.7, 
ester v. 28.9, soluble in 5 vols, and more of 90 per cent, alcohol with slight opalescence. 

From a second sample of herb, just beginning to seed, 0,034 per cent, of a brown 
oil were obtained, which had a higtier specific gravity and a higher index of refraction 
and dissolved a little better than the one before mentioned: diso 0.8795, a^-{-\o\y^ 
nD»o 1.48403, soluble in 1.4 vols, and more of 90 per cent, alcohol. 

The extremely feeble odour was remarkable with both oils. They lacked almost 
completely the l^pical smell of ascaridole, so that it is to be supposed that they con- 
tained very little of this essential constituent. This would account perhaps for the 
low specific gravity and the insufficient solubility. It is remarkable too that the oils 
were dextrorotatory. 

We are unable so far to explain these abnormalities. It is questionable whether 
they a;re only due to the absence of seeds, or whether the fact that the herb was 
grown in Germany, under conditions of climate and soil differing from those in America, 
is responsible for them. 

Since some confusion exists as to the question to which constituent of the oil 
the anthelmintic action is due, Th. A. Henry and H. Paget ^) undertook a re-examination 
of the oil. Six samples of commercial oils were used, with the constants: — d|| 0.9582 
to 0.9723, Mdiso — 45 to — 6.8^. The oils were separated by distillation under 15 mm. 
pre^ure into three fractions: — 1) b. p. below 84 ^ (25 per cent.), 2) 84 to 104 <^ (15 per cent.), 
3) 104 to 118^ (55 percent), the residue (5 per cent.) being chiefly ascaridole glycol. 
The first fraction consisted mainly of hydrocarbons, furthermore butyric acid (Ag-salt), 
methyl salicylate (below 5 jjercent.; m. p. of the salicylic acid 156°; benzoate of thcf 
ester, m. p. 83°). The hydrocarbons were a-terpinene (nitrosite, m. p. 155°), a new 
laevorotatory terpene (with the approximate constants: b. p. 177 to 178° [760 mm.], 
di6o 0.847, Mdwo—* 57°, nptoo 1.484; tetrabromide, m. p. 117°, inactive) and i?-cymene. 
The second, fraction contained hydrocarbons and ascaridole, the third consisted of 
nearly pure ascaridole (b.p. 108 to 110° [15 mm.], diso 1.0120, [a]Di50 -^ 0.5°). 

According to the statements of the authors, sylvestrene, limonene, phellandrene, 
safrole and camphor were absent. The new terpene, which could not be separated 
from «-terpinene and »-cymene, yielded on oxidation with potassium permanganate 
acetic acid, wobutyric acid and a minute amount of a volatile acid, m. p. 117°, 
crystallising in long, slender needles, but insufficient for examination. On oxidising 
a-terpinene with potassium permanganate in acetone solution, the authors obtained 
two optically inactive forms of a.ai-dihydroxy-a-methyl-a^-isopropyladipic acid (m. p. 203 



1) Joum. chem. Soc. 119 (1921), 1714. From a copy kindly furnished by the authors. 



82 Report of Schimmel S Co. 1922. 

to 204^ and 189°), which Wallach*) had obtained formerly when oxidising terpinen-4-oI . 
from marjoram oil. Wallach's acid of the m. p. 205 to 206° was, however, optically active. 
From two samples of Indian chenopodium, Ch, ambrosioides and Ch. anthdminticum, the 
authors distilled 0.17 and 0.24 percent, oil having the constants d|f|0.9399, Hduo +0,07° 



and dgo 0.9080, [«]di50 — 9.6 o respectively. 

We extract the following from P. van der Wielen's*) treatise on chenopodium 
oils: — According to the publications of Schuffner and Vervoort') American wormseed 
oil quickly gained a world-wide fame as a remedy against the widely-spread hook-worm 
disease* owing to the support of the Rockefeller Institute. Said complaint is caused 
by two intestinal worms, namely Ankyloatmna duodenale, found in the mines not only 
north of the Alps, in "France, Germany, Austria, Hungary, Belgium and England, but 
also in subtropical and tropical climates, and the perhaps still more dangerous Necator 
americanus, occurring in the South of North America, in Puerto Rico, Cuba and Brazil. 
The disease may be brought about by drinking impure water, containing larvae 6f the 
worms, or by infection through the skin. In places where the skin is thin, as for ^ 
instance on the ankles, the larvae penetrate into the body, pass through the blood- 
vessels, the lungs, the larynx and the esophagus into the digestive system and there 
develop. The miners generally get the disease in this way. 

However successful a remedy cherlopodium oil may be, its noxious qualities 
ought not tn be underrated, for it may quite unexpectedly give rise to cases of 
poisoning. In the report of the Rockefeller Institute of February 1921, Darling and 
Smillie mention three such cases, caused by a chenopodium oil that had produced 
no , ill effect with other patients. The maximum dose for grown-up people ought to 
be fixed at 3 cc. of the oil. On the other hand, the efficacity is jsaid to have some- 
times been less than expected, of proof that the anthelmintic properties of the com- 
mercial oils, the constants of which were not always the same, could be yery 
different*). 

L. Sullivan'^) has miade a detailed investigation into the manufacture of oil of 
wormseed in Carroll County, Maryland. The belt in which the wormseed (Chenopodium 
ambrosioidesj is grown, he says, extends from a short distance north of Weston almost 
due south to Woodbine, being about 15 miles long and approximately 4 miles wide. 
The plant grown outside this belt is said to be far less productive of oil, and the 
product is not so good. There are several hundred farms on which the herb is culti- 
vated systematically and gathered, the crop being taken to distilleries, of which there 
are about a dozen in the county. The largest individual farm does not exceed 13 acres, 
and the biggest company-owned plantation is about 20 acres. The annual production' 
varies from 10000 to 40000 lbs., whereas it was only 2800 lbs. in 1910 and 5000 lbs. 
in 1911. The 1920 yield is stated to have been relatively small, but the acreage culti- 
vated was larger than usual. The better the soil is worked and manured, the higher 
the percentage of oil in the plant. The yield in oil may run from 30 to 100 lbs. per acre. 

According to Chevalier*) Chenopodium ambrosioides, L., Ch. dnthelminticum, L. and 
Ch. suffruticosum, Willd., yield anthelmintic volatile oils, whereas Ch, spaihulatum, Sieb. 
and 67i. re/wswm, Moq., are less important. — Van derWielen"^) Stated that plants grown 



*) Liebig's Annalen 356 (1907), 212. — «) Pharm. Weekblad 58 (1921), 1080. As per a reprint kindly sent 
us. — *) Cf. Report 1919, 113. — *) This is quite possible, as the distillation of American wormseed oil is 
rather difficult and may lead to inferior products. Adulterations with ineffective substances are also frequent 
and sometimes even absolutely valueless artificial mixtures are offered. Cf. ^eWcA^e 1921, 53, 1920,63; £epor£ 1919, 
61, 8ic. — *) Pe/^m. Record 12 (1921), 39. — ^) Bull, des sciences pharmacologiques, Viarch 19^. — ') Jtoc. ct*. 



Commercial and scientific notes on essential oils. 83 

in India from seeds of the Chenopodium ambrodoides type yielded oils of varying efficacity. 
Whereas American oils are only laevorotatory (« — 2^49' to — 8<^50', we have observed 
—.40 to — 8^50') the Indian oils had a rotatory power of from — 2i.34o to +0.50o*). 
100 kilos of fresh herb, grown by the author in Amsterdam, yielded on distillation 
5 grams of oil. After having been rectified in vacuo at 48° (55 mm.)? its index, of 
rotation was « + 0.74°. By extraction with ether, van der Wielen obtained from Indian 
(Atjeh) chenopodium $eeds an oil, the rotation of which was «+ 1.05°. These experi- 
ments confirm Wirth's assertion that the rotation to the left increases if the oil is 
heated ]for some time^). Van* der Wielen therefore thinks it probable that an Oil of, 
Chenopodium ambrosioides, var. suffrutkosum, Willd., obtained without heating to a higher 
temperature, would be dextrorotatory or inactive, but not laevogyrate'). 

The author further calls attention to the fact tiiat other physical properties 'of the 
oil likewise alter on heating. The specific gravity decreases, the index of refraction 
rises and the solubility in alcohol and acetic, acid is lessened. The above-mentioned 
extracted oil of Atjeh seeds,"^ for instance, ha4 the following constants: diso 1.008, 
nDiso 1.4735, soluble in 5.5 vols, of 60 per cent, acetic acid. As these constants resemble 
those pf ascaridole rather much, and asi?-cymene occurs in chenopodium oil, the author's 
opinion is that on heating the oil asparidole is transformed into i>-cymene, hydrogen 
being split off. The explosion-like decomposition of ascaridole when heated, noticed 
by Kremers, is supposed to support this theory. 

Through experiments with ^nimals, M. C. Hall and H. C. Hamilton*) have proved 
that the lower-boiling fractions of American wormseed oil have the same vermifugal 
efficacity as the higher-boiling constituents, without possessing the dangerous by- 
effects as cause inflammation and bleeding of the intestines. Tijssen^) was able to 
confirm these observations through clinical experiments. He prepared by distillation 
<tf an (Indian?) chenopodium oil (d 0.968) a fraction of the specific gravity of 0.951 
and a residue of d 1.04. Both preparations were administered to patients suffering 
from hook-worm disease. In the first experiment the lower-boiling fraction resulted 
to be very efficacious, the higher-boiling one not. Later experiments had not quite 
the same result. Distillates free from ascaridole, administered three times in doses of 
16 drops ^each, ejected 77 p.er cent, of the hook-worms, whereas the fractions containing 
ascaridole, given in the same quantities, destroyed 81 per cent, of the worms. Thre 
effect on ascaridas was the same with either fraction. 

According to van der Wielen the action of the different fractions .on isolated 
intestinal worms ought to be determined, in order to refute the opinion now prevailing 
that oils of higher specific gravity are tp be preferred to those of lesser density. 
'Furthermore only the innocuous lower- boiling fractions of the oil ought to be used 
as remedies. The supposition would be very natural that the chief component of the 
lower boiling fractions, ^cymene, possessed the vermifugal properties*). 

In the meantime another publication by Henry and H. Paget'^) has appeared, in 
which they experimentally refute van der Wielen*s above opinion. The authors examined 
Hall and Hamilton's assertion (see above) that not the ascaridole but the lower-boiling 



1) Cf. also the article of Henry and Paget, mentioned before, and Bericht 1921, 15. — -) Joum. Americ. 
Phann. Assoc. 9 (1920), 127; Bericht 1920, 61. We made the s^me observation many years ago. Cf. EepoH 
April 1908, 169. Cf. also Giidemeister and Hoffmann, The Volatile Oils, 2"<i edition, vol. II, p. 360. — ») This 
seems to be too hasty a conclusion. — *) Joum. of Pharm. and Exp, Therap. 11 (1918), 231. — *) Gen. 
Tijdschr. voor Ned. Indi, AfL 1, Deel 61, 1921. — •) Taking, into consideration what other observers have 
stated, this judgment also seems a little hasty. — ') Pharmaceutical Joum. 107 (1921), 349. As per Pharm. 
Ztg. 67 (1922), 126. 

6* 



84 Report of Schimmel a Co. 1922. 

fractions of the oil, the terpenes, are the efficacious constituents. They found that 
the vermifugal action was due exclusively to the ascaridole and not to the hydrocarbons. 
The products forming on decomposition of ascaridole in the heat were completely 
inefficacious. 

E. K. Nelson'^) publishes a method which makes it jiossible to determine quickly 
the ascaridole content of wormwood oil. It is based upon the solubility of ascaridole 
/to the extent of 98 per cent, in a mixture of 60 parts of glacial acetic acid and 40 parts 
of water. The wormseed oil terpenes are insoluble in such a mixture. The test is 
carried out as follows: — 10 cc. of chenopodium oil are vigorously shaken in a cassia 
flask with 60 per cent, acetic acid. Then acetic acid of the same strength is added 
up to the mark, when the ascaridole content can be calculated from the quantity of 
undissolved oil. The author found like that in five samples from 48 to 73 per cent, 
of ascaridole. 

Ch. Sparhawk*) gives an illustrated description of three varieties of American 
wormseed (pheru^dittm awbrommdea, L., var. anthdmmUiMm, Gray). The first, wild 
variety, a tangled mass of leaves, seeds, £|c., does not produce much oil, although it 
feeds ravenously on the fertilizing material. A second, highly developed variety is 
distinguished by many seeds, with practically no leaves. This is the grade that 
produces the best oil, although the yield is not the largest. The third type, with 
stocky stem, plentiful leaves, and sEeds on short stalks, gives the biggest returns, 
but the quality of the oil is not so good. Sparhawk adds that the seeds alcne do 
not give any o\\*) but that the percentage of seeds seems to Indicate the quality. 

The superiority of chenopodium oil over thymol in the treatment of hook-worm 
disease is described in a report of the Uncinariasis Commission to the Orient'). 
Whereas there was failure to cure the patient in 23.6 cases out of a hundred treated 
with thymol, there were only 7.6 failures with chenopodium. Apart from the many 
advantages, which we have pointed out before") and the enumeration of which is 
therefore unnecessary, chenopodium oil has a disadvantage, according to the report 
in question, in that it often causes by-effects, such as dizziness, unsteadiness of gait, 
inability to rise, headache, gc. Certain purges intensified the toxic effects, thus 
giddiness and deafness were more marked among patients having castor oil than 
among those having magnesium sulphate. 

W.SchufFner and H.Vervoort') communicate that in British East India and the U.S. A. 
too large doses (3 cc) of American wormseed oil werefrequently given. Toxic effects 
(vomiting, dizziness, deafness, 8ic.) were often the result, so that the oil nearly lost 
Its good reputation in these countries. In the same degree as the doses were^radu- 
ally reduced (down to 1.2 grams), the bad by-effects ceased. According to the authors 
the age of the oil seems to have an influence on both efficacity and poisonous nature. 
Cajus and Mhaskar') found that the ascaridole content went down from 70 to 56 per cent. 
In the course of one year. Wrench") reports tiiat a chenopodium oil which, after 
having been stored for one year still contained 66 per cent, of ascaridole, had lost its 
original noxiousness, but nothing of its efficacity. If Wrench's observations are correct, 

1) Jm™. AiMiic Pftarm, djHW. 10 (1921), 836. - •) ftrf™. Keconi M (1921). 388. - •) Cf. Wirth'l 
trsaliiB {Bericht 1«S0, 60). Wirlh proved thai Ihs oil ii contained only in the hairs on the seeds and the leaves. 
— •)Fer1um.Btrordi3{\>)2\),SI. — •) CI. iiejwrt 191B, 1 13. ~ 1 MeitStetiti^n van am hurgerHjkm stneeakanrtigtit 
Dinut m >a!^atul«A.Jn'iijr ISil, I, ». — ') India« Jmn. of ninl. Beamreh IMO. — •) Ibid, IMS. 



Pharmacopceias. I 85 

oil that has been stored for some time would be preferable to the fresh product, as 
being . less poisonous. — Schuffner and Vervoprt recommend as a medium dosis three 
times 0.4 grams of chenopodium oil daily. Better results had been obtained with 
several small doses than by giving a larger quantity in one dosis. A laxative ought 
not to be given before, but after the cure. Anaemic persons should drink Karlsbad 
waters during the cure, which takes about five days. People' suffering from kidney 
or liver complaints are very sensitive and should be treated with small do§es only.. 
Chenopodium oil is said to have proved efficacious too as a remedy against 
tape-worms. v 

An article in the Apothekerzeitung also points out the danger of giving too large doses 
of American wormseed oil^). According to H. Pruning a dosis of 0.2 cc. perxkilo of 
weight was deadly for dogs, smaller doses caused paralysis, for instance of the 
respiratory organs. The oil can be given pure or in emulsions and is said not to 
have the disagreeable by-effects produced by santonin. — Children ought to have as 
many drops «is they are years old, but not more than ten, to be given after a little 
breakfast. Two hours later castor oil or another mild aperient should be given. The 
author proposes to include the remedy in the new edition of the German Pharmaco- 
poeia and to fix the maximum doses. 

The following cases show that it is not superfluous to call attention to the 
noxiousness of chenopodium oil when given in large doses: — 

A child of two years, who had taken 8 grams of wormseed otl, meant for an 
older brother or sister, died in spite of all medical assistance'). 

As per The Perfumery and Easential Oil Record^) oil of chenopodium has been the 
cause of a fatality at the Hospital for Tropical Diseases, Endsleigh Gardens, London, M.W. 

Regarding the production of chenopodium oil in Java see p. 80 of this Report. 



Pharmacopoeias. 

Italian Pharmacopoeia. 

(Farmacopea Ufficiale dd Regno d'ltcdia, ed. IV.) 

The third edition of the Italian pharmacopoeia, in use since 1910, has now been 
succeeded by a new one, the paragraphs of which concerning our articles we' wish 
to deal with in the customary manner. Unfortunately, not much favourable can be said 
'about them. Indeed, we could confine ourselves to a mere reference to our criticism 
of the former edition of the pharmacopoeia (Report April 1910, -128) since the compilers 
deemed it unnecessary to do away with the numerous faults and mistakes of the third 
edition, and in the few cases where this was attempted it was performed rather un- 
satisfactorily. Here, the compiler of the paragraph 'ought to have realised that incorrect 
statements are of but little use in commercial intercourse, as they give rise to groundless 
objections and unnecessary correspondence. There was no difficulty in eliminating the 
existing errors, if one had taken pains to look out in the respective literature. 

It may be taken for an effort to modernisation that with the essential oils notice 
has been taken of the direction of optical rotation, but since no limits have been 



1) Apoth. Ztg. 36 (1921), 375. — =) Pharm. Ztg. 66 (1921), 697. — ») Perfiim. Record 12 (1921), 185. 



>■•• 



>^. 



". .4 



86 



Report of Schimmel S Co. 1922. 









ii' 



Stipulated, this innovation is of hardly any use. In the subsequent discussion of the 
details, we have made up for this omission. 

Mo new essential oil has been admitted; cajuput oil has been struck out. 

In discussing the separate articles we follow the text of the pharmacopoeia. 

Anise Oil (Essenza di awice/ — Colourless or yellowish; daoo 0.980 to 0.990; ao ^^ 
the left^; congeals on chilling to a crystalline mass which begins to melt at 15^ and 
liquefies completely between 19 to 20 o*); soluble in 2 to 3 vols, of 90 per cent, alcohol. 
Test for phenols with ferric chloride °). 

*) The Isvorotation amounts to — 2 **. 

') Solidification must often be brought about by inoculating the chilled oil with some solid anise oil or 
anethole.^ Good quality oil begins to melt again above 17°. In case of careless storing, or after repeated 
melting the solidification point decreases constantly and the density increases. Comp. Report October 1904, 38. 

*) This test is superfluous, since it traces a sophistication never observed with anise joil. 

Cade Oil. — See Juniper Oil, empyreumatic. 

Camphor (^Caw/om/ — White, crystalline, translucent mass; dwo 0.993^); m.p.l79P*); 
bums with a sooty flame; volatile already at ordinary temperature; hardly soluble in 
water (1 :1200), readily in alcohol, ether, chloroform, acetic acid, fatty arid essential oils. 
0.1 g camphor must volatilise without leaving a residue; test for chlorine. 

Natural camphor is optically active, synthetic inactive^). 

^) This statement is quite useless, the more so as nothing is stated as to how this constant is determined. 
The value given is but only an approximate one. 

') In the S^c edition the melting point was correctly given as 175°. 

') Under certain conditions, also the synthetic preparation is active; comp. Report October 1910, 197. 

Cassia Oil. — See Cinnamon Oil. 

Cedro Oil (Esaenza di cedro^)). — Greenish-yellow, the oil obtained by distillation 
being colourless^); disc 0.857 to 0.861; "d strongly to the right*); very sparingly soluble 
in water, soluble in about 5 parts of 90 per cent, alcohol*) and in every proportion in 
absolute alcohol. ' 

') Form the specific gravity required it folH>ws that lemon oil (essenza di limone) is meant, since the- 
various cedro oils (which are no articles of commerce) are partly heavier, partly lighter than stated above. 
Compare Cildemeister and Hoffmann, The Volatile Oils, 2"<' edition, vol. Ill, p. 77. 

*) Lemon oil is usually light yellow. Oils obtained by ordinary distillation are inferior and of no 
keeping quality. 

*) The rotation amounts generally to -{-57 and -{-61 ^, oils occurring with higher or lower rotations. These data 
pertain to a temperature of 20 °, this being important on account of the change of rotation with the temperature. 

*) The solution, effected by 6 to 8 vols, of 90 per cent, alcohol, Is often turbid due to the presence of 
mucous or vegetable wax-like substances. 

Chatnomile OH (Essenza di camomUa comune). — Blue, turning brown*) when ex- 
posed to the air, or when in contact with alcoholic soda solution, disc 0.925 to 0.945; 
Roman chamomile Oil*) having d^o 0.905 to 0.915; soluble in 8 parts of 90 per cent, 
alcohol, opalescence occurring sometimes^); on chilling down to 0° it gets tough but 
does not solidify*). » 

^) Intermediately, the oil turns green. 

*) It would have been better to quote this oil separately, as it behaves quite differently from ordinary 
chamomile oil. In discussing the other details of this paragraph, we take only the latter oil into consideration. 
*) In consequence of its high content of paraffins, the oil gives but turbid mixtures with 90 per cent, alcohol. 
*) This statement is incorrect, chamomile oil being, at 9^, a comparatively solid mass. 

Cinnamon Oil (Cassia and Ceylon Cinnamon Oils) (Essenza ddla cannella). — 
Colourless or light yellow, turning gradually into yellow or brown*); soluble in 3 parts 
of 70 per cent, alcohol^; dioo with Ceylon oil 1.024 to 1.040; ao to the left»); di5o with 



Pharmacopceias. 87 

Cassia oil 1.055 to 1.065^). Reactions with nitric acid and with ferric chloride; per- 
centage of cinnamic aldehyde not below 70*). 

^) Cassia oil is from the beginning daric yellow to brown ; neither of the two 'cinnamon oils are colourless. 
^) With cassia oil, the solution is in most cases not quite clear. 

*) Up to —1^, rarely higher. With cassia^oil, the rotation amounts up to —\^ and -f 6^. 
*) The upper limit is given too low, it must read 1.070. 

*) This does not apply to either of the oils. With Ceylon cinnamon oil, the aldehyde content amounts 
to 65 to 76 per cent.; with cassia oil, the lowest value is at least 75 percent. 

Clove Oil (Essenza di garofani), — Yellowish, turning gradually brown when exposed 
to the air; duo 1.045 to 1.070; soluble in 2 parts of 70 per cent, alcohol; eugenol per- 
centage at least 85 when tested with 5 per cent, caustic potash solution^); identity 
reaction and test for absence of phenoP). 

^) The amount of caustic solution required by the pharmacopoeia is insufficient. This fact has equally 
been pointed out by V. Massera {Biv. Ital. ddle easenze e profumi 3, Jan. 12, 1921; ace. to Chem. ZmtraVbl.lVZi, 
II. 171) who suggests to shake, in a cassia flask, 10 cc. oil with 100 cc. 3 per cent, caustic soda solution. 

*) Adulterations of clove oil with phenol have n^ever been observed hitherto. A note on the rotation 
might have been useful, clove oil rotating to the left, up to —\^35\ 

Eucalyptole (EuccUiptdo). — Colourless; disc 0.930*); b.p. 176 to 177°; solidifies, 
in a freezing mixture, to a crystalline mass which remelts at — 1<^*); identity reaction 
with bromine; when mixed with the same volume of carbon disulphide eucalyptole 
must yield a clear mixture (test for water); test for phenols- with ferric chloride ')f 

^) The specific gravity ranges between 0.928 and 0.930. 

*) Eucalyptole melts at about 4~V°' '^ necessary, congealing musf be started by rubbing the glass walls 
with a glass rod. ' \ 

*) This test' is unnecessary, on the other hand, it might have been pointed out that eucalyptole must 
be inactive. 

Eucalyptus Oil (Essenza di mcalipto). — Light yellow*), oq exposure to the air it 
turns brown and resinifies; di6o 0.910 to 0.930; «© faintly to the right'); soluble in 3 vols, 
of 70 per cent, alcohol; percentage of eucalyptole not below 70, tested by the resor- 
cinol method*). 

^) Eucalyptus oil is colourless, pale yellow,, or pale greenish. 

^) The rotation amounts up to -{-15^. 

'> The pharmacopoeia prescribes our original test of shaking 10 cc. oil with 90 cc. of a 50 per cent, 
resorcinol solution. Since sometimes too high figures are obtained hereby, we later on modified the method. 
Compare Reports April 190B, 50 and October 1915, 20. 

Juniper berry Oil (Essenza di ginepro). — Colourless or faintly greenish yellow, 
thickening on exposure to the air and light and turning then more yellow; diso 0.865 
to 0.885*); soluble in 9 parts of 90 per cent, alcohol*) and in 1 part of carbon disulphide®). 

^> The lower limit is given too high, it must read 0.860. > 

*) Only freshly-distilled oils answer this requirement; the solubility decreases rapidly. 

') A possible turbidity is caused by a slight content of water due to the preparation of the oil. Here, 

too, a reference might have been made to the optical rotation, the latter being to the left and amounting usually 

up to — 13*>, rarely higher. 

Juniper Oil, empyreumatic (Cade Oil) (Olio cadino),— Dark brown ; d^o 0.99 to 1 .05 ; 
sparingly soluble in water to which it imparts an acid reaction; soluble in ether, 
chloroform, and absolute alcohol; miscible with carbon disulphide and benzine only 
with turbidity; about 65 per cent, of the qil must distil between 150 and 300^; identity 
reactions. 

Lavender Oil (Essenza di lavanda). — Colourless*), faintly yellow or green; 
di6o 0.882 to 0.895; a^ to the left; soluble in 3 parts of 70 per cent, alcohol; percentage 
of linalyl acetate, at least 35; test for absence of citric ester'). 



s. 



88 Report of Sghimmel S Co. 1922. 

^) Only the rectified oils are colourless, these, however, being of inferior quality. Comp. Gildemetster 
and Hoffmann, The Volatile (His, 2"" ed., vol. HI, p. 434, footnote 2. 

*) The rotation ranges , between —3 and —9°. 

') This test should have been extended to other esters which may likewise be present besides ethyl 
citrate. Comp. Gildemeister and Hoffmann, The Volatile OUSy Z^^^ed., voj. Ill, p. 441 and Bericht (German) 1920, 39. 

Menthol (Mentolo).--^ Colourless prisms; m. p. 44°*); b. p. 21 2°*); neariy insoluble 
in water, most readily soluble ih alcohol, ether, chloroform, and carbon disulphide, 
soluble in fats and paraffin oil; 0.1 g. menthol must not leave behind a welghable 
residue when evaporated on a water bath; test for absence of thymoP); 

^) A pertain allowance must be granted, t. e., 42 to 44^. 

*) Menthol boils under 753 mm. at 215^, the mercury thread being wholly surrounded by the vapours^ 

*) Since mixtures of menthol and thymol are liquid this adulteration is highly improbable. 

Methyl Salicylate (SedicUate de metilej. — Colourless; soluble in alcohol, ether, 
paraffin oil, fatty and essential oils; scarcely soluble in water: di5o 1-182 to 1.187*); 
b. p. 218 to 221°. On* shaking with water the volume of tbe ester must not decrease 
to a noticeable extent (test for absence of methyl or ethyl alcohol); identity reaction 
with ferric chlorides. 

*) The limits are incorrect, the specific gravity ranging between 1.185 and 1.190 (15°). 

Mustard Oil, natural and artificial (Essenza di senape). — Colourless, afterwards 
yellowish with a tinge of red; b. p. 148°^); disc with the artificial oil 1.020, with the 
natural oil 1.018 to 1.025*);, "d + O^; readily soluble in alcohol, ether, and carbon 
disulphide, sparingly soluble in water (1:1000); identity reactions; percentage of iso- 
thiocyanallyl, 94 to 99. ^ ' 

^) This requirement must read correctly, mustard oil boils /br the greater part between 147 and 153^. 
*) This statement is likewise incorrect; the specific gravity of the artificial oil is between 1.020 and 
1.025, that of the natural oil between 1.014 and 1.025 (150). 

Orange Blossom Oil (Essenza di fiori d'arancio amaro). — Yellow, turning reddish 
under the influence of air and light; blue fluorescence; diso 0.870 to 0.880; ap to the 
right*); soluble T to 2 parts of 90 per cent, alcohol; on adding more opalescence ensues*). 

*) French neroli oil, the chief commercial product, rotates between -fl^SO' and 4-9° 8', Spanish oil 
between -j-9<>30' and 4-29 o, Italian oil between +2° 54' and -}- 56° 30'; the two last-named oils are, however, 
in all probability no pure distillates from the flowers of the bitter orange. 

^) This statement applies for 80 per cent, alcohol; in 90 per cent, alcohol, orange- flower oil is clearly 
soluble in every proportion. After some time, however, slight opalescence sets in owing to a separation of paraffin. 

Peppermint Oil (Essenca di menfa). — Colourless, straw-yellow, or greenish, on 
exposure to the air turning gradually yellow and viscous; disc 0.890 to 0.920; disc of 
the Italian oil 0.908 to 0.925; «!> strongly to the left^); English oil dissolves in 3 to 
5 volumes of 70 per cent, alcohol, Italian oil gives with about 2 volumes sometimes 
a slightly opalescent solution which does not become clear on further dilution'); 
solidifying at — 8 to — 20^ with separation of menthol, Italian oil does not solidify 
even at —17^; colour reaction with glacial acetic and nitric acids'); test with iodine 
for absence of turpentine oil*). 

1) The rotation ranges between —20 and —34°, with Italian oils between —2° 30' and —260 51'. 

*) American oils which, to judge from the specific gravity, are equally official, give generally a faint 
opalescence of the solution; with English oils this is sometimes likewise the case. 

') We consider it decidedly a failure to comprise such a reaction (to which evpn otherwise normal 
English oils do not always answer) amongst the requirements of a pharmacopoeia. The quality of an oil musts 
never be judged by this reaction. It would have been far more correct to require a definite minimum content 
of menthol which with good commercial oils is not below 50 per cent. 

^) This test is entirely superfluous, quite obsolete, and absolutely useless, and ought to have been 
abandoned in the prior editions. 



Pharmacopceias. 89 

Rosemary Oil (Essenza di rosmarino). — Colourless or yellowish-green; di5o 0.90 
to 0.92; soluble in 10 parts of 90 per cent. alcohoP). 

^) Rosemary oil dissolves already in one-half volume of 90 per cent. alcohoL 

Sandalwood Oil (Essenza di sandalo), — More or less yellow; disc 0.975 to 0.985*); 
etjy to the left*); soluble in 5 parts of 70 per cent, alcohol; santalol (Ci6H24 0) content 
not below 90 per cent.^). 

1) The lower limit should be 0.973. 
*) The angle of rotation lies between —16 and —20°. 

') This minimum content does not agree with the statements given in the pharmacopoeia as to the 
estimation of santalol which correspond to a content of 87.26 per cent. 

Terpine Hydrate (Terpina idrata). — Lustrous, colourless and odourless prisms; 
on drying in a vacuum or above sulphuric acid it loses about 9.5 per cent, water; 
soluble in about 250 parts of cold, in 32 parts of boiling water, or in 10 parts alcohol, 
insoluble in light petroleum; the aqueous solution must show neutral reaction; terpine 
hydrate melts at 116^, terpine at 102^*); on boiling the aqueous solution acidified with 
sulphuric acid a smell of hyacinths*) is produced; 0.1 g. terpine hydrate must burn 
without leaving a residue. 

- 1) Terpine melts at 104 to 105o. 
*) In this reaction, terpineol is formed which, however, smells of lilac and not of hyacinth. 

Thymol (Tiwo/oj. — Colourless, translucent crystals; m. p. 49 to 50°*); b. p. 228 
to 230°'); sparingly soluble in water (about 1:1200), the aqueous solution must show 
neutral reaction; soluble in less than 1 part of alcohol, ether, acetic acid, chloroform, 
and fatty oils; soluble in 2 parts of .10 percent, caustic soda solution; melted thymol 
^ floats on- water, solid thymol drops down; 0.05 g. thymol, when heated on the water- 
bath, must volatilize completely; identity tests and test for absence of phenol. 

*) The m. p. lies between 50.5 and 51.5°. 

*) Thymol boils, under 753 mm. pressure, at 232°, the mercury thread being fully surrounded by the vapours. 

Turpentine Oil {Essenza di tremeniinu). — Colourless; boiling range, 155 to 162°; 
di6o 0.860 to 0.877; «d to the right or the left according to the origin of the oil ^) ; 
perfectly volatile; hardly soluble in water, soluble in 12 parts 90 per cent, alcohol, 
7 vols. 94 to 96 per cent, alcohol, in every proportion of absolute alcohol, ether, chloro- 
form, carbon disulphide, fatty and essential oils'); resinifies when exposed to the air; 
neutral reaction; when kept in a bottle but partly filled the oil turns yellow and shows 
acid reaction. 

For certain purposes, the crude oil is admitted, which is colourless or faintly 
yellow and leaves on evaporation a residue of 2 per cent.^. 

In addition, old, so-called ozonised oil must be kept for use, which colours blue 
a paste of starch and potassium iodide. 

*) The rotation ranges between -f 41° and —35°. 

^) Possible turbidity is caused by a small amount of water in the oil owing to the distillation process. 
On addition of a desiccating substance, e. g., sodium sulphate, such turbidities disappear instantaneously. 

') This evaporation must be performed with special precautions, as otherwise too high values may result. 
Compare Gildemeister and Hoffmann, The Volatile Oils, 2"*' ed., vol. II, p. 20, 




•*r ^'fM 






Report of Schimmel a Co. 1922. 






Chemical Preparations and Drugs. 

Benzaldetiyde. — In our last Bericht^) we accurately described our method of 
quantitative determination of chlorine in benzaldehyde. The apparatus then shown in 
the picture, and supplied by the Leipzig firm of F. Hugershoff, has meanwhile been 
slightly modified. 

Both the U-tubes serving as absorbing vessels have been provided with a short 
pipe each which can be closed by means of a piece of rubber tubing and a pinch- 
cock, so that the absorbing liquid can now be more easily removed. Furthermore, 
the glass tube connection the two U-tubes has been provided with a small bulb, as 
sometimes the liquid of the first U-tube passed over into the second. 

In addition we would mention the fact that the air in the laboratories is liable to 
contain hydrochloric acid gas and that then even passing it through dilute silver 
nitrate solution may not free it entirely from chlorine. We therefore connect the 
apparatus with the fresh air outside by means of a glass tube passed through a small 
opening in a window. ' , ' 

As previously mentioned*) we consider the indication of "beOzaldehyde, technically 
tree from chlorine" as a nuisance, liable to cause confusion to the detriment of the 
honest dealer. Our opinion has since been confirmed, for its is almost jncredible 
what stuff is frequently offered under above designation. There are products of all 
shades, from a slight to the most pronounced chlorine reaction, and it is only a 
matter of how elastic the conscience of the supplier may be for terming the product 
"technically" or, as it is now called, "commercially free from chlorine". 

Out of the many samples which have been examined in our analytical laboratories 
we would only mention one, just to show what amount of cheek some suppliers have. 
The constants were as follows: diso 1.0633, f^n + O^b^ nowo 1.54054, completely in- 
soluble even in 10 volumes of 50 percent, alcohol, acid v. 12.5 = 2.7 percent, benzoic 
acidf chlorine reaction: extraordinarily strong. This shows that the article was absolutely 
unsatisfactory, not a single one of the constants coming up to the requirements for 
benzaldehyde. It is even too bad for a crude product, as results from the defective 
solubility and the excessive specific gravity, which latter cannot be explained by an 
excess of benzoic acid, into which benzaldehyde may be converted by oxidation. These 
two properties referred to induced us to examine the sample a little more closely, as 
far as the small quantity permitted. It resulted that the product contained only 68 per cent. - 
of benzaldehyde. The quantity at our disposal was not large enough' for further in- 
vestigation regarding the admixtures, Sc. 

W. von Rechenberg*) prefers Beilstein's copper oxide test for chlorine in benz- 
aldehyde to the well-known combustion method. After comparative tests, he ascribes 
more exact results to the former. 

We have stated on previous occasions^) that, in our opinion, the combustion 
method is decidedly more accurate and reliable than the copper oxide test, and we. 



1) Bericht (German) 1921, 56. — «) Ohem.-Ztg. 45 (1921), 627. — ») Eejyort April 1912, 151 



Chemical Preparations and Drugs. 91 

Still adhere to this standpoint. We consider Beilsteins*s test as useful only for general, 
guidance, and it seenis risky to us to deduce binding conclusions from it in all the 
cases, as owing to the perceptible volatility of the copper benzoate the flame may be 
coloured green by; the benzoic acid, which would lead to erroneous conclusions*). We 
would therefore recommend caution when judging benzaldehyde by the result of the 
copper oxide test. 

As to catalytic reduction of benzaldehyde wjth copper,- and the pyrogenous de- 
composition of benzaldehyde, see pages 131 and 146 of this Beport. 

Benzylalcohol. — According to D. J. Macht and A. T. ShohP) solutions of benzyl- 
alcohol k^ep their anaesthetic qualities unchanged when kept in ampoules of unattackable 
glass, and their hydrogen ion concentration varies but very showly., On the other 
hand, ii) glass which gives off alkali the solutions loss their anaesthetic power quickly 
and show alkaline reaction in the course of several months. 

I. Messner') gives the following explanation for the decomposition of benzylalcohol 
which is said to pass off also in neutral or feebly acid (acetic or hydrochloric acid) 
solution: — Apparently, reduction as well as oxidation takes place simultaneously, one 
molecule of the alcohol losing oxygen with formation of toluene, a second molecule 
absorbing the oxygen liberated with formation of benzaldehyde and water:— 2C0H6CH2CH 
= CeHsCHg + C0H5CHO + H2O. This reaction may be accelerated by action of light, 
or dwing to the presence of organic or inorganic impuritijcs in the water or the benzyl- 
alcohol. The latter can even be its own catalyst, as has been proved by Jacobson. 
Messner strongly disapproves that aqueous solutions of benzalcohoji which decompose 
easily, be traded in ampoule fillings. 

By heating benzylalcohol, in xylene solution, with barium sulphate -|- palladium 
K. W. Rosenmund and F. Heise*) obtained 5 per cent, benzaldehyde, 12 per cent, benzyl 
ether, 50 per cent benzylalcohol, and 20 per cent, undistillable residue. Pure barium 
sulphate was of no influence on the alcohol. 

The action of the benzyl esters on the human or the animal organism may be 
attributed either to the unchanged benzyl ester molecule or to the benzylalcohol formed 
in the body by hydrolysis of the ester. The fact that benzyl acetate and benzoate are 
excreted as hippuric acid and that benzylalcohol has a relaxing effect on the unstriped 
muscle seems to indicate that the effect is due to the hydrolysis of the esters*'). Hence, 
it would be rather probable that the- therapeutic effects would be proportional to the 
rates of hydrolysis of the esters. This possibility induced E. H. Volwiler and' E. B. Vliet*) 
to investigate the- chemical part of the problem and to compare the rates of hydrolysis 
of a number of benzyl ethers. Their experiments, which were conducted according 
to the directions of Bischoff and Hedenstrom'), proved that the rates of hydrolysis of 
the esters, under identical conditions, increase in the following order: — salicylate, 
benzoate, stearate, cinnamate, acetate, succinate, and fumarate. In benzyl acetylsali- 
cylate, the rate of hydrolysis is of the same order as in benzyl salicylate. 

The authors give a description of the methods employed for the preparation of 
some of the esters. The preparations had the following constants: — fumarate, m. p. 58.5 



1) Cf. Kunz-Krause, Apotheker-Ztg. 30 (1915), 141. IJepor* October 1916, 56. — *) Joum. ofPharm.and 
exper. Therap. 16 (1920), 61. As per Therap. Halbmonatsh. 85 (1921), 216. — *) Pharm. ZentrdUi. 68 (1922), 1. 
— *) Berl. Berichte ^ (\92\), 20A2. — ») Macht, ./oum. P/iarmacol. 11 (1918), 263. — *) Joiim. Amer. chem. 
Soc. 48 (1921), 1672. — ») Berl. Ber. 85 (1902), 3433. 



92 Report of Schimmel S Co. 1922. 

to 59,5^, b. p. 210 to 21 1° (5 mm.); salicylate, b.p. 170 to 175o (7 mm.); cinnamate, 
m. p. 33 to 340, b. p. 228 to 230^ (22 mm.); acetylsalicylate, m. p.' 25.5 to 26.0^, b.p. 197 
to 2000 <7 mm.). 

Benzyl Benzoate. — E. C. Mason and E. C. Pieck^) did not notice any change worth 
mentioning in the respiration of dog^ after an intravenous injection of 2 cc. of 10 percent, 
benzyl benzoate solution; breathing became flatter after an injection of 4cc., the blood 
pressure decreased and, the, contractions of the pylorus became feebler. The latter 
ceased altogether after an injection of 6 cc. (the breathing stopped at the same time, 
causing death). The solution had only a slight effect on the tension of the small 
intestine; lage doses may cause hearth failure. The action on the uterus was very 
feeble, the increase of the pressure in the artery of the lungs inconsiderable, whereas 
no extension of the bronchioles could be proved. 

According to E. A. Heller and E. Steinfield*) daily injections, repeated for four 
days, of 1 cc. each and one injection of 1.5, 2 and 2.5 cc, respectively, of benzyl 
benzoate per kilo of weight had no effect on the number of white corpuscles in rabbits. 
After larger doses the animals became sleepy and faint, one of them died. 

» 

Bromostyren^. — Theoretically, three monobromostyrenes substituted in the side- 
chain are possible, i. e., the two stereoisomerides with the formula Ph • CH : CHBr and 
the body Ph-C3r:CHs. Two isomerides are hitherto known, namely one <w-bromo- 
styrene PhCH:CHBr (A) and the a-bromostyrene PhCBnCHa (B). Ch. Dufraisse') 
succeeded in obtaining the third isomeride, the other ft'-bromostyrene (C), from bromo- 
benzalacetophenone and powdered caustic soda*, m. p. —8 to — 7^; b.p. 71° (6 to 
7 mm.); d2oo 1.426; njja^o 1.5990. Phenylacetylene resulted aS by-product. Furthermore^ 
the author obtained, by heating sodium dibromohydrocinnamate with sodium carbonate, 
according to Nef*), the well-known ^w-bromostyrene (m. p. +6 to 7°^); b.p. 107° (22 to 
23 mm.); djoo 1.422; nDM.^© 1.6094), and from phenylacetylene and hydrogen bromide, 
a-bromostyr^ne, m. p. — 43°; b.p. 71° (7 to 8mm.); daoo 1.406; np^.s© 1.5881. 

With alcoholic potash solution the three bromostyrenes yield phenylacetylene. 
The bodies A and C, on treatment with bromine, gave rise to identical tribromostyrenes 
PhCHBr-CHBr2, m. p. 37 to 38°; thus the constitution of the three bromostyrenes as 
given above is proved to be correct. 

The two geometrical isomerides of the m. p. +6 to 7° and — 8 to — 7°, according 
to observations by the same author*), undergo most readily a mutual but partial 
rearrangement under the influence of sun-light. Strangely, the sftable form (m. p. +7°) 
obtains equilibrium sooner than the other modification. The mixture of the iso- 
merides, when equilibrium is reached, melts at +2° and shows the same odour as 
the stable form. 

On exposure to the air, «-bromostyrene is readily oxidised to bromoacetophenone. 
Since freshly-distilled a-bromostyrene shows no irritating action on the mucous mem- 
branes, Dufraisse'^) is of opinion that the irritation caused by older preparations must 
be ascribed to the presence of bromoacetophenone. 



1) Joum. ofLahorat. and Clin. Med- 6 (1920), 62. As per Chem. ZentralU. 1921, III. 495. — «) New York 
med. Joum. 112 (1920), 160. As per Chem. ZentralU. 1921, 1. 507. — «) Compt. rend. 171 (1920), 960. — 
*) Liebig'8 Annalen 808 (1899), 267. — ») With our own preparations we observed: — sol. p. i0to2.5O; the 
m. p. stated above must therefore be regarded with some suspicion. — ^ Compt. rend. 172 (1920), 67. — 
') Ibidem 172 (1921), 162. 



Chemical Preparations and Drug?. 93 

Camphor. — D. A. Wallace and S. B. Plumer^) determined the amount of camphor 
in camphorated oils by heating the solution in cotton-seed oil for three hours, that in 
V pea-nut or olive oils for four hours and that in sesame oil for five hours up to 120° 
and calculated the camphor content from the loss in weight. Camphorated oils are 
oxidized on heating and increase in weight. This increase in weight, which has been 
, determined by the authors in certain cases, has to be taken into account when 
calculating the camphor content. 

The authors further recommend the already known method^) of determining the 
the camphor content in camphorated oils by means of the optical rotation. 

Castoreum. — At the annual auction in London, the Hudson Bay Company offered 
in December 1921 2649 lbs. of Canadian castoreum, of which 575 lbs. were sold. Of the 
Oregon quality 2932 lbs. were available, of which 1170 lbs. were disposed of^). 

Coumarin. — According to a process invented by W. Ponndorf *) coumarins are 
obtained by condensing phenols or phenol ethers with fumaric or maleic acids under 
the influence of condensing agents such as zinc chloride, or aqueous or alcoholic 
73 per cent, sulphuric acid, at a temperature not below 120*^. The condensation of fumaric 
acid with phenols passes off by union of a hydrogen atom in oriho position of the 
phenol with one of the two COOH-groups of the acid, with formation of formic acid, 
and by ring-formation of coumarin from the resulting coumaric acid. ^ 

T. Yanagisawa and H. Kondp*), in preparing coumarin, make use of iodine as 
catalyst, and obtained, when boiling salicylic aldehyde, acetic anhydride, and sodium 
acetate for four hours in an oil both, a yield of 70 per cent, crude coumarin. 

G. C. Bailey and F. Boettner*), when endeavouring to prepare methylcoumarin from 
malic acid and m-cresol, found the method devised by Fries and Klostermann ') to be 
the most successful one. They obtained the highest yield (54 per cent.) of methylcumarin 
when malic acid Was added slowly to a the mixture of m-cresol and sulphuric acid 
heated to 135°, the reaction product then poured on ice, and the precipitate formed 
taken up in 50 per cent, alcohol and crystallised from this solvent. A m-cresol of 
84 per cent, yielded about 40 per cent, of methylcoumarin. 

Toxicity tests carried out with mice proved methylcoumarin to be not more than , 
one-tenth as toxic as coumarin. As to the perfume value, dilute solutions of methyl- 
coumarin were said to be of almost the same odour* as those of natural coumarin. The 
odour of the dry crystals, however, was considerably less intense than with natural or 
synthetic coumarin. 

■ • _ . 

Eucalyptole. — The cresineol method for the determination of cineole devised by 
T. Tusting Cocking®) gives, according to recent statements®) of the author, satisfactory 
results if the amount of cineole present in the sample reaches 45 per cent, and upwards. 
When the amount of cineole present falls below 45 per cent, the method must be 
modified insofar that a certain amount of pure cineole, or an equivalent amount of 



1) Am&ric. Pharm. Journ. 93 (1921), 600. — «) Cf. Reports April 1916, 73; 1918, 92. Some angles of 
rotation arc given for the Oils mentioned, with and without camphor. — *) Oily Paint and Drug Beporter 
101 (1922), No. 1, p. 32. — *) Germ. Pat. 338737, published July 4, 1921; Chem. Zentralbl. 1921, IV. 1224. 
— ») Joum. pharm. Soc. Japan 1921, no. 472; Chem. ZentraTbl. 1921, III. 958. — •) Journ. ind. eng. Chem. 18 
(1921), 905. — ') Cf. Bejiort October 1906, 96. — «) Comp. Rericht (German) 1921, 65. — ») PerfUm. Record 
12 (1921, 339. 



M 



>-j«^?>>:f' 



^■K'^^ 



if! 












94 



Report of Schimmel S Co. 1922. 



pure cresineol is added to the oil before carrying out the determination. The result is 
calculated by means of a table, with due regard to the cineole or cresineol added. 

According to this modified method the author tested a series of oils with low^ 
cineole content, with the following results: — 



Percentage esters 

Lavender oils, French ... 29 to 52.7 

„ „ English ... 6.2 „ 10.7 

Spike oil$ 2.3 „ 3.9 

Rosemary oils, French . . . 3.1 and 4.1 

oil, Spanish ... 2.5 



n 



Percentage cineole 

18.0 to 22.6 
23.6 „ 27.4 
33.2 „ 39.0 
23.2 arid 25.4 
19.4 



We abstain from discussing the correctness of these figures, yet we find the 
quantity of cineole found by Cocking in the French lavender oils remarkably high. 
According to our own observations*), French lavender oils contain only very small 
amounts of cineole, and we come to the conclusion that Cocking must have dealt with 
adulterated, or highly impure oils. Should this not be the case, the results would 
certainly not speak in favour of the cresineol method, which, too, was originally devised 
for different purposes. In such a case, the statements concerning the cineole content 
of the other oils would have to be regarded with some doubts. 

Gum Benjamin. — A. Mayrhofer*) examined a gum benjamin offered by a Vienna 
firm as Palembang benzoin and sent in tins of 15 kilos. The drug which ought to alter 
quickly its appearance when the pieces are broken and left in contact with the air, 
consisted of reddish-gray to gray-brown pieces which easily crumbled and showed on 
some larger surfaces the impression of white pieces of tissue. The neighbouring pieces 
of gum were gray or blackish. The main part of the substance was composed of pieces 
of wood, held together by a whitish or brownish-red, glossy mass. After exhaustive 
extraction with alcohol there was a residue of 52 to 68 per cent. No cinnamic acid 
was present (test with potassium permanganate). As to benzoic acid, 3.1 per cent. 
= 9 per cent, of the part soluble in alcohol, were obtained. The alcoholic extract had 
the following constants: acid v. 99.9 (determined indirectly), saponification v. 198.1 
(determined in the cold). The microscopic examination of the pieces of bark showed 
that they originated from a Styracea. 

The available data were therefore not sufficient to characterize the drug as Palembang 
benzoin, especially because the n^other plant and origin of this commodity are not 
known well enough so far'). Nevertheless the article is said to have a certain value, 
as it may be useful, for instance, for preparing benzoin tincture. 

Heliotropin. — The oxidation of t^osafrole to heliotropin is considerably favoured 
by the addition of amino-carboxylic acids. On the strength of this fact C. Sievers and 
L. Givaudan ^ Co.^) publish a process, consisting in that 120 parts of i^osafrole are 
oxidized at a medium temperature with a solution of either sodium bichromate 



^) Comp. Report October 1898, 27. Por safety's sake, we endeavoured to prove or determine, with four 
lavender oils of warranted purity, the cineole present and arrived at the result, in accord with our former 
experiences, that lavender oil contains but so little cineole, that the proof of its presence causes some 
difficulty. There is absolutely no possibility that pure lavender oils contain such an amount of cineole as 
stated by Cocking. — *) Apotheker Ztrj. 86 (1921), 821. — ') According to LOdy and Tschirch Palembang 
benzoin is exported from Palembang in Sumatra; Dieterich mentions as mother-plant a Styracea of Further 
India, about which nothing definite is known. — *) Swiss Pat. 91087, Oct. 17, 1921. Addn. to 89053. Cf. 
p. 99 of this Report. 



\ 



Chemical Preparations and Drugs. 95 

(240:1000) or chfomic acid, in the presence of 10 parts of i?-amino-benzoic acid, 
dissolved in 460 parts of 50 per cent, sulphuric acid. By way of the bisulphite compound 
one obtains 15 parts of unaltered i^osafrole and 90 parts of heliotropin. 

Menthol. — The list of articles which the Board of Trade considered dutiable 
under the Safeguarding of Industries Act includes menthol. We do not know what 
prompted the competent authorities to take this remarkable step, as an article is 
concerned which gannot possibly be made in England. Anyway this proceeding has 
roused a storm of criticism in the affected quarters in England^), so that the Board 
of Trade tried to get out of all difficulties by adding the letter "R" to menthol, which 
signifies that the chemical indicated is included only when it is "pure'', "puriss.'^ 
"extra pure", **B. P.", Sc. In criticizing this measure the Chemist and Druggist gives 
vent to the following opinion: "There is no specially purified menthol obtainable in 
cpmmerce, except as a laboratory curiosity, and then it has no superiority over ordinary 
menthol." If the author knew that purified, le. recrystallized menthol is sold in ton 
lots on the continent and that, contrary to what may be the case in England, Germany 
and a good many other European countries use n6 other menthol at all for pharma- 
ceutical purposes, he would surely have given a different verdict. . ' 

Further communications on menthol are to be found under the heading of Japanese 
Peppermint Oil^ page 58 of this Eeport. 

^' Musk. — Chungking is the chief port of original export for musk, which is brought 
into Szechwan from Tibet, says Consul P. R. Josselyn, Chungking*). During the ten 
years from 1893 to 19Q2 the fiverage yearly export through the Maritime Customs at 
Chungking was 3971 pounds, while during 1918 the amount exported was only 948 pounds. 
This decline was partly due to the war; but for the last 15 years there has been a 
steady decline, which would indicate that the musk deer is no longer as plentiful or 
as easily caught as formerly^). Probably considerably less than one-half of the musk 
that comes into China from Tibet is exported abroad. The remainder is used locally 
by the Chinese medicine shops and as a perfume. 

Before the war France took approximately 50 per cent, of the export, the United 
States being second, taking about 20 per cent. During the five yearsfrom 1910 to 1914 
the average yearly export to the United States from all China was 406 pounds, valued 
at 120284 Haikwan taels*). During the three years 1915 to 1917, inclusive, it increased 
to 613 pounds, valued at 195087 Haikwan taels. 

Musk, artificial.— According to A. Reclaire**) a "new brand of musk", received 
from France, contained no less than 82 per cent, acetanilide. For the quantitative 
determination of this well-known adulterant of artificial musk the author proceeded as 
follows, basing his method on the prescriptions given by A. Seidel^) and J. C. Tonus'): — 

The acetanilide is decomposed by boiling it with 20 per cent, hydrochloric acid. 
The aniline formed is converted into tribromo-aniline by means of an excess of 
potassium bromide-bromate solution of known strength. After having added some 
potassium iodide solution, the excess of bromine is titrated back with sodium thio- 
sulphate solution, when the content of aniline (acetanilide) can be calculated from 



^) Chemist and Dniggist 95 {\92\), 875. — «) Awcrtc. Pe»/tmierlG (1921), 106. — ») Cf. -Bmc/i* (German) 
1920, 72. — *) As to the altered value of the Haikwan tael see Bericht (German) 1920, 73. — ») Perfiim. 
Beeord 12 (1921), 280. — •) Joum. Americ. ehem. Soc. 29 (1907), 1091. — ') Physisch-chemisch onderzoeic van 
verbindingen, gevormd uit een amine en een organiscfi zuur (Leiden 1918). 



r.7. . 






IS;;- 96 Report OF ScHiMMEL S Co. 1922. 

{,! ' the difference. This method is said to be sufficiently accurate for te^"*^^^ purposes 

(difference 0.4 to 0.6 per cent.). * 

O. Wichmann^) examined trinitroi«obutyltoluene and trinitrobutylxylene^^ *^ ^^^^^ 
|- pharmacodynamic action. In the human or animal organism, by oxidatic?" ^^ ^® 

|h'; CHs group, the trinitrobutyl toluene splits off water which joins the butylglP^P* ^" 

§!.; f this way tertiary butyl alcohol is formed in addition to *n-trinitrobenzoic acii- ^^^ 

latter combines with glycocol, thus forming m-trinitrohippuric acid which is'sec^^®^ 
with the urine. The tertiary butyl alcohol has the capacity of combining in the aniSD^* 
organism with glycuronic acid which also leaves the body with the urine. The humaf? 
organism secretes the tertiary butyl alcohol through the respiration process. \ 

In a closed room, insects (gnats and flies) were killed by the effect of artificial musk. > 

A subcutaneous injection of 0.05 to 0.1 gram of trinitrobutyltoluene dissolved in 
oil caused the death of cold-blooded animals (frogs) after four hours. 

Warm-blooded anim.als were not affected by up to 1 gram taken internally. After 
a subcutaneous injection of 0.2 gram dissolved in oil an increase of the reflex move- 
ments was noticed in guinea-pigs; 0.4 gram caused death within 12 hours after previous 
signs of paralysis. 

Doses up to 1 gram, internally, had no effect on human beings; but it is to be ^ 

supposed that larger quantities injected subcutaneously must act as poison on the \ 

human organism. 

A therapeutical use of trinitrobutyltoluene and trinitrobutylxylene is not very likely ^ 

to come into consideration. 






\ 



* 



\ 



Myrtole. — The myrtle oil fraction boiling between 160 and 180° is used for 
inhaling under the name of myrtole. One of its essential components, which causes 
perhaps its praised antizymotic and desodorizing effect, is eucalyptole. This con- 
sideration apparently induced the supplier of a so-called myrtole, submitted to us for 
inspection, to give eucalyptole instead, a proceeding requiring a rather elastic conscience. 

The sample behaved as follows:— d^o 0.9294, Od + Oo, riD»o 1.45802, solidification 
point + 0.2^, soluble in 4 volumes and more of 60 per cent alcohol. These constants 
tally completely with those of eucalyptofe (djBO 0.928 to 0.950, «DibO°, nD»o 1.454 to 
1.459, solidification point between and +1°, soluble in 4 volumes and more of 
60 per cent, alcohol, whereas those of myrtole are entirely different, as is shown by 
the following figures established for myrtole of our own distillation: — dis© 0.884 to 
0.904, "0 + 15 to +24°, nDwo 1.462 to 1.463, soluble in 0.5 volume and more of 
90 per cent, alcohol, sometimes already in 80 per cent, alcohol (1 to 2 volumes). \. 

The difference in price between myrtole and eucalyptole is so considerable, that ' 
above supplier's tactics paid well, even if he sold his "myrtole*' very cheap. 



4 



Nitrobenzene. — We mentioned in our last Bericht*) that freshly marked linen 
caused symptoms of poisoning in babies. We are now told^) that they were not due 
to nitrobenzene, but to aniline. 

In two cases of acute poisoning with nitrobenzene, due to "Jamaica gingers" con- 
taining this body, R. F. Loeb, A. V. Bock and R. Fitz*) examined the blood* Methaemo- «j 
globin was not present; the oxyhasmoglobin in the arterial blood was reduced to 6.2 

*) Dissertation, Bonn 1921. As per Apoiheker-Ztg. 96 (1921), 510. — «) Bericht (German) 1921, 67. — 
») Deutsche med. Wochenschr. 47 (1921), 1526. As per <?Aem. Zentralbl. 1922, I, 480. — *) Americ. Joui-n. of the 
Med. Sciences 161 (1921), 539. As per Chem. ZentralU. 1921, III, 968. 



Chemical Preparations and Drugs. 97 

It, the capaci^ of binding oxygen to 8.9 and 6.2 p^r cent., respectively. 
derate leucocytose and, for six hours, anuria. In the urine ;j-amino- 
escnt 

case of poisoning mentioned was brought about by resorption through 
[arments had been soiled with oil containing nitrobenzene). 

detection of nitrobenzene in bitter almond oil, see page 6 of this Report. 

iam. — A balsam of Peru, sent us for examination, was greatly adulterated 
ted to be a composition, but was termed genuine by the supplier, who 
e it back, in spite of the repeated reclamations of the buyer. As the 
I large concern and in a position, no doubt, to have the article properly 
: case is a perfect riddle for us. If one had taken the trouble to look 
into tne maticr, the determination, of the specific gravity would have revealed already 
that there was something the matter. 

Said balsam behaved as follows^^duo 1.1387, cinnamein content 63.6 per cent., 
ester v. of the cinnamein 225.4, nitric acid test = bluish green colouring. There 
could not be any question of a pure, genuine balsam. Its specific gravity and the 
ester v. of the cinnamein were too low; besides, the cinnamein differed from the 
normal product in that It was not liquid at room-temperature, but semi-$oHd. The 
nitric acid test, leading to a golden yellow colouring in the 'case of genuine balsam 
of Peru, also Indicated adulteration. 

For any expert the stuff would have been suspicious on account of its odour and 
abnormally light colour. It is .therefore remarkable, that the supplying concern tn 
question did not notice anything. Needless to say that such a concoction does not 
answer the requirements of the pharmacopoeia. 

Peru Balsam, artificial. — We have taken up the manufacture and are pleased 
to state that our product meets with increasing popularity. 

Bark of Rhamnus Prangula. — Through steam distillation of the bark ol Rhamnus 
iVangida, O. A. Oesterie') obtained 0.05 to 0.1 per cent, of a crystalline substance of 
strongly fusty smell, which had probably formed only during the distillation. The 
product contained, apart from dark coloured impurities, small quantities of a white 
crystalline body, insoluble in soda solution; a compound precipitated in the form of 
a jelly from hot soda solution; a body soluble in soda lye, crystallizing from water 
in radiate form, and a compound insoluble In soda lye, crystallizing from alcohol In 
the shape of brownish yellow scales. This inodorous and tasteless substance had 
the empiric formula CuHnOi, m. p. between 100 and 101°. 

Resin of a Peruvian Styracea. — E. Maldonado*) examined a resinous substance, 
known in the Province of Cuzco (Peru) by the name of imienso macho and frequently 
used for incense, perfumery and medical purposes. The drug comes probably from 
a variety of Styrax {Styrax ooatv/m, A. DC, occurs in the valleys of Cuzco, Umbara 
Valley) and forms irregular, hard, reddish-black or black masses. They are covered 
with a greenish dust and taste aromatic at first, then sharp. The fractured surface 
exhibits a brilliant, vitreous, yellow colour. The odours recalls that of vanilla. The 

1) Bot. Farm, de Lima of luna 30", IWO. Ai per CTiemirf and Dmggiat 96 (1921), 207. 



98 Report of Schimmel S Co. 1922. 

author prepared from the drug a gum, an oxydase, va;>illin, a small quantity of aromatic 
esters, and 5 per cent, of benzoic acid. 

Thymol.— The Badische Anilin- und Sodafabrik in Ludwigshafen publish a method 
of preparing thymol from n»-cresoP). The tn^cresol is sulphonated, and the resulting 
m-cresol-sulphonic acid treated with i^opropyl alcohol and sulphuric acid (preferably 
concentrated) in the warmth. The sulpho-group is split off the mass at a temperatufe 
of from 120 to 125°, the thymol being distilled off simultaneously. The oil thus 
obtained, which is almost completely soluble in dilute soda lye, is treated in the 
usual way and subjected to fractionated distillation. The first runnings cont^iin the 
unaltered cresol, then the thymol passes over, whereas the last fraction contains 
probably an isomeride of thymol, crystallizing from benzene in large crystals (m. p. 114 
to. 1150)1 

• 

The preparation of thymol from cymene has repeatedly been patented already "). 
R. M. Cole*) suggests as a further improvement the electrolytic reduction of nitro- 
cymene and the subsequent diazotisation and reduction of the l-methyl-2-amino-4^o- 
propyl-5-hydroxybenzene. The diazo-group is then replaced with hydrogen in the 
usual w^. 

Nothing is mentioned in the discussions as to the yield. 

By condensation of one molecule of salicylaldehyde and two molecules of thymol 
in the presence of some dilute sulphuric acid, F. Lavilla Llorens^) obtained hydfoxy- 
phenyldithymylmethane 0H-C6H4CH :(C6H2-CH3 0HC8H7)8, m. p. 1850; methylether, 
m. p. 137 to 138*^; ethylether, m. p. 77 to 78°. In these compounds all the three 
hydroxyl-groups reacted. Tribromo derivative, m. p. 170°; iodine derivative, m. p. IIIP. 
By double interaction of the alkali derivatives with metal salts the lead, copper and 
iron compounds were obtained. 

According to R. Maire*^) the following three species of Ptychotis occur in North 
Africa: — 1, Ptychotis Ammi, |L. = Sison Ammif L. = Seseli ammmdes, L. = Ptychotis 
amnuMeSj Koch, a small annual plant occurring so abundantly in fallow ground that 
one might think it was cultivated. This umbelliferous plant, found in all southern 
Europe, is easily recognized by its smooth, naked stems and leaves, its petiolate 
pinnules and its white inflorescences provided with dimorphous bracts but without 
any involucre. 2. Ptychotis trachysperma, Boiss. = P. aspera^ Pomel., is distinguished 
from the former by its wrinkled fruits and its spatulate bracts. It occurs in western 
North Africa and in Spain. 3. Ptychotis atlantica, Coss., a perennial flowering late and 
occurring frequently in the higher mountains (Tell Mountains in the departments of 
Algiers and Constantine; Aures Mountains). All the parts of these plants smell 
strongly of thymol, especially the fruits, and might perhaps be used for the manu- 
facture of this phenol. 

Brocq-Rousseu^) mentions that horses can stand internal doses of 0.22 to 0.25 gram 
of thymol per kilo. From 0.20 gram upwards symptoms of paralysis occur. The 
symptoms of poisoning are faintness, ataxy, fall of temperature and often paralysis of 



1) D.R.P. 350809 of July 4*^, 1980. — «) Cf. Berichte (German) 1920, 77; 1921, 74. — ») Per/iim. Record 
12 (1921), 281. Chem. Zentralbl. 1921, IV. 513. — *) Ann. Soc. Espanola Fia. Quirn. [2] 18 (1920), 139. As per 
Chetn. Zentralbl. 1921, III. 785. — *) Parfum. modeme 14 (1921), 79. — •) Compt. rend. soc. de biologic 84 
(1921), 257. As per Chem. Zentralbl. 1921, III. 125. 



m 



■f 






Chemical Preparations and Drugs: 



the hind-legs. If the thymol stays for any length of time in the stomach or in the 
intestins, it irritates the mucpus membranes. Aristol (dithymoldiiodide) is soluble in 
water and in the gastric juice. - 

Vanillin. 'H. C. Sievers and L Givaudan S Co.^) publish a method of preparing 
vanillin from acetylisoeugenol by oxidation with sodium bichromate or chromic acid, 
in the presence of amino-carboxylic acids. The addition of 1.5 to 2 per cent, of such 
a amino-carboxylic acids as catalyst, for instance ^amino-benzoic acid, has a favourable 
influence on the oxidation and on the yield of vanillin. One proceeds as follows: 
120 parts ofxt^oeugenol are distributed in 1240 parts of a sodium bichromate solution 
(250 parts in 1000 parts of water); under continuous stirring at a temperature of 80°, 
a solution of 1.5 to 2 parts ofjp-aminobenzoic acid in 500 parts of 50 per cent, sulphuric 
acid is allowed to flow in. As soon as the oxidation is completed the acetylvanillin 
formed is extracted with a solvent and the vanillin obtained by way of the bisulphite 
compound. One obtains 12 parts of unaltered acettsoeugenol and 68 parts of vanillin. 

The yield is the same if the amino-carboxylic acids are replaced by aromatic athino- 
aldehydes, such as i?-amino-benzaldehyde*). 

As to the manufacture of vanillin from guayacol land formaldehyde, see page 143 
of this Report. 

Two samples of vanillin tested in our laboratories were grossly adulterated; one 
contaifiing about 55 per cent, of antifebrin, the other 75 per cent, of benzoic acid. 
The adulterants influericed the melting point considerably, of course, for the preparation 
containing antifebrin melted already between 64 and 68 <^ (instead of at 82°), whereas 
the other began to sinter at 68° and was completely melted only at \\0^. 

The antifebrin was sejJarated off by shaking the product, dissolved in ether, with 
soda lye, when only the vanillin is taken up by the sioda lye. The antifebrin remained 
in the ether and was obtained by^ evaporating the solvent, it was recognized by its 
melting point (113 to 114°) and by its wonitril reaction. 

The benzoic acid was separated in a similar way, only that in this case the vanillin 
was removed from the ethereal by shaking it with bisulphite lye. The residue obtained 
on evaporation of the ether melted at 121° and coiild be identified as benzoic acid 
also by its other properties.' 

Taking into consideration the difference of price between vanillin and these two 
adulterant^ one easily understands that the buyers of the article will have paid far too 
much for it in spite of the apparently low price. 

The methods of vanillin determination in vanilla extracts^), according to which lead' 
acetate is added to the dealcoholized extract and the aldehyde is the determined by 
weight, often lead to inexact results. Either the vanillin obtained is not quite pure and 
ttie figures are too high, or the purification causes losses. The method indicated by 
Hiltner^), who purifies the vanillin in the end through sublimation at 105°, is not perfect 
either, as according to H. |. Wichmann'^) the aldehyde forms non-volatile decomposition 
products, when heated for some length of time to the above temperature. Wichmann 
heated pure vanillin for 3 to 6 hours at 105 to 108°, and obtained 4 to 5.6 per cent, 
of non-volatile, yellowish-brown residues, most likely oxidation and decomposition pro- 



*) SuH88 Patent 89053 of April 16*", 1921. — «) Stoiaa Patent 91088 of October 17*", 1921. Supplement 
to 89053. — *) The alcoholic extract of vanilla is meant. — *) JJ. S. Bur. Chem. Bull. 152 (1912), 135; 162 
(1913), 83. — ») Joum. Aas. Qffic. Agric. Chem. 4 (1921), 479. 



•'■. •■■■^^ 
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ducts of a complex nature. This indicates that the errors caused by the sublimation 
of the vanillin according to Hiltner*s method, are considerable in the case of vanilla 
extracts containing more than 0.2 per cent, of vanillin. 

Winton and his co-workers devised a lead number, now the official A. O. A. C. 
method, for analyzing vanilla extracts. In Wichmann's*) opinion it is not free from 
objection and he therefore publishes a new method of determining the lead number, 
supposed to simpler and more reliable. 

To 175 cc. of boiled water in a liter flask Wichmann adds 25 cc. of 8 per cent, 
lead acetate solution and 50 cc. of vanilla extract, removes the alcohol by distillation, 
adds dilute sulphuric acid to the diluted and filtered residue and calculates the number 
of grams of metallic lead in the lead sulphate precipitated. This figure doubled is 
the required lead number. 

Doherty') says that the gravimetric determination of vanillin in vanilla essences 
can be avoided by a method based. upon the reaction of the aldehyde with sodium 
bisulphite and the colour reaction with bromine water and ferrous sulphate. The author 
states that it is reliable and easily carried ont with the aid of Duboscq's colorimeter. 
A detailed description is given in the Chemiker-Zeitung 45 (1921), 687. 

Thiercelin and Violet^) give the following information regardihg the solubility of 
vanillin: Vaselin dissolves 11, glycerin 7 and oil 11 per cent, of vanillin at the ordi- 
nary temperature. 



i'- 


Temperature 


i.-' '■ ■ 


10° . 


¥■-■ 


20° . 


W- 


50° . 


M''' ^ 


780 . 


lo.^ 


We f< 


|;;.- .. 




fe"/" ' 


«f 1 < 



Water 



Solubility of Vanillin per litre. 



Alcohol 



15 per cent. 

50 grams 

66,6 
166,6 
400 



30 per cent. 60 per cent. 

'80 grams 755 grams 



i> 



n 



n 



1500 
3000 
4000 



n 



n 



n 



90 per cent. 

1 100 grams 
1750 
5000 
10000 



n 



n 



. . 5,2 grams 

. . 15,5 „ 66,6 „ 180 

. . 44,4 „ 166,6 „ 750 

. . 66,6 „ 400 „ 950 

We found, the following proportions*): — 

Solubility of Vanillin in 100 parts by weight of the solvent at 10°., 

Alcohol 96 per cent. Alcohol 70 per cent. Glycerin Olive Oil Liquid Paraffin 

38 grams 30 grams 1 gram 0.9 gram less than 0.1 gram 

The vanilla crop in Madagascar, Comores and Reunion, amounting to 500 tons on 
an average, is estimated at only 350 tons for 1921. It is supposed that the United 
States consume 35, France 25, England 10, Switzerland 8, Scandinavia 8 and Germany, 
Holland and Spain together 14 per cent, of the crop^). 

The following data are taken from an article on vanilla production in Mexico by 
Ch. H. Cunningham*): — At present Mexico employs over 50000 people in the cultivation 
and extraction of vanilla. Vanilla iyanUla planifoliay Andr.) is indigenous to the soil 
of Mexico^). It is principally cultivated in the districts of Papantla and Misantla in the 
State of Vera Cruz, the most productive region lying south-east of Tuxpan, between 



*) Americ. Perfumer 16 (1921), 301. — *) Joum. and Proceed. Royal Soe. of New South Wales 67, p. 157. 

— ') Par/um. modeme 14 (1921), 153. — *) BepoH April 1909, 144. — ») Dnig and Oiemical Markets 9 
(1921), 405. — •) Commerce Beports, of November 20*", 1920. As per Americ. Joum. Pharm. 93 (1921), ^2. 

— 7) Preuss considers the wild Mexican vanilla to differ from Vanilla planifolia. Berichte d. Pharm. Chtt, 
11 (1901), 24. 



Chemical Preparations and Drugs. 101 

the river§ Nantla.and Tuxpan. French colonists who settled on the banks of the Nantla 
river in the 19*^ century learnt the cultivation of vanilla from the natives and were 
soon successful. (According to Preuss^) the plantations were in a bad state in 1900 
but have been enlarged continuously since.) The vanilla grows best in rich, sand soil, 
not drained too thoroughly, at an altitude of 1000 feet above sea-level. It is sheltered 
by the trees of the forest or by trees planted for that purpose. 

There are different varieties of vanilla in the vicinity of Misantla. They are not 
so plentiful nor are they considered so good ks the Papantla beans. These indigenous 
varieties are the dmarror, the mestiza and the mansa. When they are cured, only an 
expert can distinguish between the various classes. There is also a wild bean known 
as vanilla platano, which the Indians eat. This differs from the ordinary vanilla in that 
the plant is much smaller but has larger leaves. 

In order to avoid plundering of their crops, the planters cut the vanilla early, 
sometimes in October and November instead of in January, and February. As a result 
the beans weigh a pound less per thousand than they would normally. 

For commercial purposes vanilla is divided into four classes: grande Jina (20 cm. \ 
chka fina (10 to 15 cm.), za^ata and basura. The former two differ only in length, 
whereas their weight is almost the same. The ^^acafa, which is a larger bean than the 
forifner two, grows more abundantly along the roadsides in the warm and hot regions 
of Mexico, where formerly it was considered to be without commercial value. 

The exports from Mexico were as follows: in 1912/13 = 288766 kilos to the value 
of 3315471 Pesos; 1918 = 45066 kilos to the value of 505020 Pesos; 1919 = 197403 kilos 
to the value of 2333264 Pesos. 

According to W. M. Doherty*) Mexican vanilla beans average 2 per cent, Java and 
Bourbon beans about 2.75 to 2.9 per cent, of vanillin. Tahiti vanilla is but of little 
value in comparison, sis it contains only 0.6 to 0.7 per cent, of vanillin. 

Guadeloupe vanilla is generally classed among the inferior kinds') although it may 
come very near the Mexican product if properly treated. As Ch. A. Smeltzer®) states 
the Guadeloupe planters have generally not cured the beans carefully enough nor in 
the proper way, so that their commercial value suffered. The Guadeloupe vanilla begins 
flowering in March, at which time the flowers are fecundated by the natives, who use 
a small wooden instrument (similar to a tooth-pick). Quite often the natives fecundate 
too many flowers on the same raceme with the result that the beans are apt to be 
thin and short. Another disadvantage is that the native planters gather the beans often 
immature (it takes about nine months for the vanilla to ripen). When thoroughly cured, 
this immature vanilla will result in a dry, ordinary quality bean ; but the average curer, 
who is curing for weight and not for quality, permits the moisture to remain in the 
bean, with the result that his product reaches the market in apparently good condition, 
but soon gets mouldy. On the other hand, the fully-matured bean will never lose its 
good quality. 

Frequently the beans are cured in Guadeloupe by the hot water method, which 
involves the smallest loss in weight. However, only the Mexican or sweating method, 
introduced in the island already 30 years ago by M. Fox, leads to a first class vanilla. 
Smeltzer has the beans assorted first and then "needled*\ This 'is done by making four 
scratches on the outer suriace of the bean from end to end, deep enough to break 
through the skin, in order to permit the moisture to escape. This enables the bean to 



1) Joum. and Proceed. Royal Soc. of New South Wales 57, p. 157. As per Chem. Ztg. 46 (1921), 696. 
2) Cf. Seports April 1902, 100; October 1909, 142. — *) Americ. Perfumer 15 (1921), 197. 




1 



\. 












d? 



tir-' 



Report of Schimmel ft Co. 1922. 

cure uniformly within as well as without. About 10 o'clock in the morning woolen 
blankets are spread on cement terraces, which by this time have become hot from the 
sunshine, each blanket being capable of holding about 25 kilos of green beans. Weather 
permitting, the various sized green beans are spread on the blankets and allowed to 
remain until 2 p. m. Then they are wrapped up in the blankets, folded tightly and turned 
upside down. After an hour's heating in this manner, the bundles are deposited in 
"sweating boxes" specially made to hold 500 kilos and not to permit any of the heat 
to escape. After 48 hours the boxes are' opened and the vanilla is carefully gone over 
for mouldy beans. The others are again taken to the terraces, placed on other dry 
blankets and again given the sun. This heating and sweating process is repeated from 
eight to ten times, until the beans give off no more moisture and are sufficiently cured. 
The finished beans are dried on wire trays for two weeks, then assorted and packed 
into tiruB lined with wax paper. 



1 
j 

1 



/ 



Notes on scientific research. 103 



Notes on Scientific Research in the Domain of the 

Terpenes and Essential oils. 

Geiieral. 

In. a paper on the Oils, Fats and Waxqs in Latin America, O. Wilson^) gives 
a description of the principal essential oils manufactured in these countries. For the 
most part thuy are the products of the tropical regions of northern South America, 
Mexico, Central America, and the West Indies, the value of which products is but 
small compared with the resources. In Mexico, linaloe oil is distilled from the wood 
and also the )seeds of various species of Bursera, in French Guiana the Cayenne 
linaloe oil from "bois de rose femelle'^ a strong-smelling wood said to derive from 
Ocotea caudata, Mez., a lauracea, and likewise the so-called Guiana sandalwood oil 
from wood originating apparently also from different lauraceae^). A similar oil, the 
so-called West Indian sandalwood oil, derived from the rutacea Amyris balsamifera, L.'), 
has been shipped to Europe for over a century. It has been used as adulterant of, 
and substitute for, genuine sandalwood oil. The West Indies furnish furthermore 
orange oil (|amaica), pressed and distilled oil of limes (Montserrat, Jamaica, Dominica), 
bay oil (Jamaica, St Thomas, Guadeloupe, Antigua, Barbados, and Dominica), and 
pimento oil (Cuba, Haiti, Trinidad, San Domingo, Antigua, Leeward and Windward 
Islands, and Jamaica). The evergreen pimento tree, Pimenta officinalis, Lindl., also 
occurs in Mexico, Costa Rica, and Venezuela. Other possibilities of Jamaica, not yet 
developed, include vetiver and - camphor. In Paraguay, the great number of bitter 
orange trees are made use of for the preparation of bitter orange oil and, to a limited 
extent, also of neroli oil. Another tree, the zygophyllacea Bidnesia Samdentif Lor., 
growing in Paraguay and Argentina, yields the important guniac wood oil, called 
erroneously also "champaca" oil*). 

Other essential oils and materials from which they can be distilled cover a wide 
range throughout the tropical forests of the Amazon and Orinoco Valleys and French 
Guiana. In Brazil, the leaves of a plant called "false jaborandi", Arthante genicidata, 
Miq. (PtperacecBjj yield a light-greenish oil of spicy mint-like odpur and pungent Jburning 
taste; the leaves of Citrosma oligandra, Jul. (Monimiacece) , called in Brazil "^ catingueira*\ 
furnish an oil with a greenish fluorescence and an odour resembling bergamot. The 
leaves of the wild lemon, Citrosma cujahana, Mart. (Monimiaceoe), contain an oil with 
an odour of bergamot and lemon, and those of the wild coffee tree, Citrosma Apiosyce, 
Mart., an oil with a lemon-like odour. From the bark of Dicypdlium caryophyUatum, 
Nees, "Cassia curyophyllata^\ an oil is obtained containing eugenol and having a clove- 
like odour. In Bolivia, a grass grows abundantly which is closely related to lemon- 



^) Chem, and met. Eng. 34 (1921), 1101. — Bull, of the Pan-Amer. Union, October 1931, 334, where the 
same article is put>lished with two additional illustrations (evidently drawings) of the Paraguay petitgrain oil 
industry which are omitted in the Chem. it met. Eng. — *) Cf . Report October 1911, 80. — ») Cf. Gildemeister 
and Hoffmann, The Volatile Oils, 2"C ed., vol. Ill, p. 114. — *) Genuine champaca oil has entirely different 
qualities and originates from Michelia Champaca, L. 



104 Report of Schimmel § Co. 1922. 

grass and citronella grass and yields an oil similar to that of vetiver. In British 
Guiana and Brazil, the branches of the priprioca tree (Ocotea preciosa, Nees, LauracecB — 
female pfiprioca^)) contain an oil somewhat resembling linaloe oil. From Brazil, Venezuela 
and Colombia, copaiba balsam, from Salvador largely balsam of Peru, and from Colombia 
principally balsam of Tolu are exported. Mexico and Central America yield oil of 
turpentine. Finally,. we mention vanilla and tonka beans which are grown in Mexico and 
the West Indies, and in Venezuela, Trinidad, Tobago, the Guianas, and Brazil respectively. 

The National Committee on medicinal plants and plants yielding essential oil and 
extracts growing in Italy and the Italian colonies published a report^) on its activities 
in 1915 to 1919. The Committee was formed at the beginning of the war in order to 
propagate thei cultivation and utilization of medicinal plants in Italy. The report 
enumerates the following plants, the cultivation of which come under consideration: — 
Peppermint, calamus, common and Roman chamomile, cherry laurel, lavender, balm 
(melissa), rosemary, thyme, valerian, anise, cumin, eucalyptus, fennel,' rose, sage, and 
violets.— In the surroundings of Naples, and in general on the south coast, inter alia, 
various rose varieties such as Jtosa Hayi, M. Briinner^ B. damascena^ R. centi/olia, 
R, Drushy were cultivated. Since the cultivation would appear to pay — the oils 
extracted with ether were very fragrant — , it is intended to be continued. From fennel 
seed, melissa and laurel leaves, the blossoms of Origanum mdgare, L and the leaves 
of Lippia citriodora, H. B. et K., the Institute of pharmaceutical Chemistry at the Naples 
University obtained, by distillation, a good yield of the essential oils. 

A publication by W. W. Stockberger') deals with the cultivation of drug plants in 
the United States. In numerous places in the Central and Eastern States the following 
drug plants have been found to thrive well: — anise, belladonna, caraway, chamomile, 
conium, coriander, digitalis, dill, elecampane, fennel, henbane, horehound, sage, stram- 
onium, tansy, and thyme.— Aconite, arnica, lovage, poppy, senega, valerian, and worm- 
wood seem to thrive best in the northern part of the U. S. where the rainfall is well 
distributed. On the other hand, cannabis, licorice, and wormseed are better suited 
to the warmer climate of the South. — Alethris, althaea, angelica, calamus, orris, 
pinkroot (Spigdia marUandica, L.), peppermint, serpentaria, and spearmint are adapted 
generally for situations where the soil is rich and moist, but lavender and larkspur 
prefer well-drained sandy soil. Ginseng and goldenseal (Hydrastis canadensis, L.) occur 
naturally on rich soil in the partial shade of forest trees. In addition to the plants 
mentioned, the following have further been cultivated: — cascara sagrada, castor-oil 
plant, Pyrethrum dnerariaefolium, Trev., Lobelia inflata, L, parsley, pokeweed^ safflower, 
saffron, vetiver, wintergreen, and wormseed. 

In a paper entitled, "Michigan, an important source of faw vegetable products'*, 
H. Kraemer*) reports on cultivation experiments started with about 50 drug plants in 
the botanical gard^ of the university of Michigan. As the experiments turned ont 
satisfactorily, Kraemer advocates a more extensive cultivation of the plants in Michigan. 
Of aromatic plants, spearmint and, above all, peppermint have been cultivated in that 
State. The peppermint oil industry, the development and history of which the author 
relates in full, started originally in Wayne County, New York, and was introduced into 
Michigan, Indiana, Ohio, and other states later. The climate and soil of Michigan 



*) Cf. Bepori April 1911, 87. — *) Federazi(me pro MontibtM, Pubblicazione N<» 94, Rome, 1921. — 
•) U. S. Dep. Agr., Fanner's Bull. 663, August 1920. — *) Mich. Acad. Set. BepoH No. 21, 1919. As per a 
reprint kindly forwarded to us. 



Motes on scientific research. 105 

proved to be particularly favourable for the growing of peppermint, and the oil industry, 
therefore, developed here preferably well. The world's annual production of peppermint 
and spearmint oil amounts to about 600,000 lbs. Of this quantity, America — and 
principally Michigan — produces nearly one-half. Each acre yields about 30,000 lbs. of 
the green herb, which when distilled furnish to the utmost 100 lbs. of oil. 

As to the origin of the peppermint industry, Kraemer's narrative runs as follows:— 
About 75 years ago there was a Yankee pedlar named Burnett who went through the 
country districts of Connecticut, Massachusetts, Vermont, and Mew York peddling tin- 
pans, rugs, chromos and other articles coveted by the farmeif's families. The women 
had not a great deal of money, so Burnett hit upon a scheme of exchanging herbs 
in lieu of money for his merchandise. It} the course of his travels he secured such 
quantities of peppermint so as to distil the oil by constructing numerous stills, 
especially in \yayne County, Mew York; he then gave up his peddling business and 
devoted himself to collecting and distilling the mint. Seeing the success of Burnett, 
a dealer H. G. Hotchkiss*) became interested in the peppermint oil industry, sold the 
oil (not touched by American drug dealers) to Hamburg realising thereby a good 
profit, and soon started to work on an extensive scale. The farmers of Wayne County 
followed his example, and in a short time the industry spread throughout the county. 

A preliminary statement of the general results of the 1919 census of manufactures, 
for the essential oil industry of the United States, has been issued by the Bureau of 
the Census, U. S. Department of Commerce*). In 1919, 77 establisliments (1914:103) 
produced essential oils (not included are synthetic and artificial oils) valuing S 441 1 775 
iS 1289361). In Michigan, 29 establishments were located in Michigan, 22 in Indiana, 
9 in Connecticut, 5 in Mew York, 4 in Mew Jersey, 3 in Pensylvania, 2 in Virginia, 
and 1 each in California, Kentucky, Ohio, and Tennessee. 

According to the Census for 1920^), the total quantity of flavours produced in 
1920 in the U. S. showed a reduction by 73 per cent, compared with the production 
in 1919, due principally to a greatly diminished output of saccharin and coumarin. 
Mew flavours reported in 1920 were benzyl acetate, benzyl cinnamate, cinnamyl pro- 
pionate, ethyl cinnamate, methyl phthalate, and "vanilidine'\ 

The production of perfume materials was 99470 lbs., valued at S 332008 (138 per cent, 
gain compared with the value in 1919). The number of preparations increased from 
24 to 41. The following were reported for the first time in 1920: — acetophenone, 
anisic aldehyde, cinnamic aldehyde, diphenylmethane, ethyl benzoate, ethyl phthalate, 
wobutylphenyl acetate, methyl benzoate, methylethyl acetate, methyl cinnamate, methyl- 
indole, phenylpropyl acetate, styrene, isobutyl salicylate, methyl guaiacol, benzylidene 
acetone, and j^-cresol methyl ether. 

We cull the following statements from a report*) of the Experimental Station for 
aromatic plants in Madagascar, located in Iroloina, near Tamatave, near the eastern 
coast of the island. 

The cultivations in Mossi-B6 of the ylang-ylang tree started some years ago**) but 
given up later on have been started afresh in the last years although the blossoms 
are considered to be inferior to the Manila blossoms. Quite recently, the geranium. 
Pelargonium roseum, Willd. has been cultivated in Madagascar, hithertho with good 



^) H. G. H. is to-day one of the oldest American trade marks, but it comprises only crude oil. — 
«) Drug and chem. Markets 8 (1921), 1055. — •) Census of dyes and coal-tar cJiemicals 1920, 49. — *) As per 
HeiU und Geunirzsflamen 4 (1921), 126. — ■) Cf. Report October 1909, 124. 



106 Report OF ScHiMMCL S Co. 1922. 

success. From the Mbramanga and Fianarantson districts^ large quantities of geranium 
leaves are exported. In the island of Mayotte belonging to the Comoro Islands, in 
the north-west of Madagascar, the cultivation of mint, sage, verbena*), and especially 
patchouli has been starred. 

The clove tree, Caryophyllus aromaticus, L.,/ is very common in Madagascar, parti- 
cularly in the rainy district of Ste.-Marie, Movrantsatra, and Tamatave. In 1918, 
200 tons of cloves were exported from Ste.-Marie. 

The principal export commodity of Madagascar is the vanilla bean, which is culti- 
vated in the north-western coast and the volcanic districts of the island, in Nossi-Be, 
and the Comoro Islands. In Antalaka, on the northern coast of Madagascar, the annual 
turnover of vanilla amounts to 100 tons. In order to drain the fever districts and to 
protect other cultivations, the eucalyptus tree, E, Globulus, Lab. has been successfully 
grown in many parts of Madagascar. Likewise, nutmeg trees (Myristiea fragruns, Houtt.) 
are cultivated in several places of that island. ' , 

Of wild-growing aromatic plants of Madagascar, the following may be mentioned: — 
the hazamalanga tree, the fruit of which is said to contain an oil with a strong aro- 
matic oiP); Ravensara aromcdica, Gaertn., a lauracea with aromatic leaves and bark; 
AngrcBcum fragrans^ Thou., an orchidea, the leaves of which, smelling of coumarin, 
are used for scenting tea; finally, a Canarium species with a fragrant resin. 

According to an article In The CJiemist and Druggist of Australasia^ the large 
plant installed by G. J. Adcock in New South Wales for the preparation of the essential 
oils of orange, lemon, lavender, geranium, and. peppermint appears to meed with good 
success. Wages in Australia are low compared with those in other countries, and a 
further advantage is the encouragement given by the Excise regulation^, which permit 
the use of duty-free Australian spirit provided it is converted into the primary perfume 
by adding other Australian products so as to effectively denaturise the spirit. 

Some thirty-five years ago the Victorian Government established a "perfume farm" 
which was at first remarkably successful, but owing to lack of interest on behalf of 
the new Goverment, turned out a. failure after some time. A sad mistake, too, wais 
that the French methods for obtaining oils had been copied, e. g, the **enfleurage k 
froid'^ process, withouth due regard to their suitability for Australian products, and 
even without exact knowledge how these processes were to be carried out properly. 

According to a note in the Chemiker-Zeitung*), the Spanish distillers of essential 
oils refrain from distilling large quantities of oils, more especially of thyme oil, owing 
to their unfavourable financial situation, and the slow deipand of Spanish oils ruling 
since October 1920. The principal buyers of thyme oil are the Americans who prefer 
the oil of TomUlo cardsqusnOf a Corydothymus species growing in Southern Spain and 
rich in carvacrol, while the French patronise the oil from TomUlo rojo (Thymus mdgaris, L.) 
with but 20 to 47 per cent, of phenols, of which 30 to 35 per cent, thymol. 

A question in this respect was kindly answered by Mr. Felix Gutkind*^), Malaga, 
as follows: — The statements in the Chemiker-Zeitung are perfectly correct. Only very 
little rosemary oil has been distilled; but this oil can be distilled at any time of the 
year, except in the months with excessive rainfall, so that the stocks, when scarce. 



^) Prom the abstract available it is not clear whether it is the case of the true verbena, Lippia citrio- 
dora, H. B. et K., or of the so-called Spanish verbena. Thymus hyemalis, Lange. — ') From hazamalanga 
wood, Bois de Cass, originating from Hemandia peltata, Meissn. of Madagascar we obtained years ago 1 .03 to 
2.06 per cent, oil with an odour of perilla aldehyde. The oil obtained from the fruits (0.5 per cent.) did not show 
this odour. — ») Chemist and Druggist 95 (1921), 48. — *) Chwn.-Ztg. 45 (1921), 776. — ») Letter of Aug. 31, 1921. 



Notes on scientific research. 107 

can be renewed within a short time. The only question is whether the cutters are 
willing to suffer a reduction of their wages as long as the victuals remain so dear in 
Spain. In many cases, rosemary oil has been sold to foreign countries with loss or 
at least without profit merely with the object to secure , means for distilling thyme oil, 
the yield of which was likewise very low as pompared with former years. 

France and equally England^ it is true, have' purchased a good quantity of oil 
rich in .thymol, since both -countries make use of thymene (? a mistake in lieu of 
thymol). The U. S. are and were buyers of Corydothymm oil sampled to you recently. 
Much of this oil is also shipped to Grasse. In the preceding years, the bulk of the 
oil from Thymm vulgaris in Spain has been worked up for thymol production. 

As to the result of the yield of spike oil, nothing definite can be said as yet. 
High-priced stocks from 1920 stilf exist. The 1921 crop will most certainly be but 
one-fourth of the 1920 one, and the 1921 production is most probably to be limited 
by the owners of old stocks with the view to justify the high price of the old crop 
as soon as a lively demand appears. 

As per a report of the Administration of Mysore^) for the year ending |une 30, 1920, a 
number of satisfactory essential oils are distilled there. Important results were obtained in 
the distillation of cardamoms. Nearly two tons of patchouli leaves were distilled, and the 
oil was used for perfumery purposes. Qualitative experiments were done in the distillation 
of rosha grass, vetiver, lemongrass, citronella grass, Kasturi arsina^ and ajowan seeds. 

J. A. Hugues *) gives a description of an apparatus serving for extracting the 
odorous p^nciple with volatile solvents from plants, roots, leaves, flowers, even from 
gums(!) and resins. Two endless movable chains circulate within the extraction pan 
and carry a series of boxes which travel continuously from top to bottom and vice 
versa^ as in a dredging machine. The extractor contains a sufficient quantity of liquid, 
such as light petroleum, carbon disulphide, or ethyl chloride, so that the lowest box 
at a time is completely submersed in the solvent. The bottom, lid, and the side walls 
of each box are perforated. The boxes are then filled with the drugs for extraction 
and worked continually through the solvent until the latter is saturated with the perfume. 
The major part of the solvent is then drawn off by means of a pipe at the bottom of 
the still, and by distillation the liquid is separated itrto solvent and odorous residue. The 
solvent retained by the drug may recovered by steam-distillation of the boxes. Owing 
to the low loss of solvent this process seems to be preferred to other methods *). 

A. Koehler"^) has constructed a contrivance for abstracting automatically the odorous 
principle from flowers. The flowers are fed from a hopper on a circulating greased belt 
running over two cylinders. After a certain time the flowers are stripped off from the belt. 

The recovery of essential oils from the distillation tvaters by cohobation is stated, 

in a communication by J. de Lorgues*), to have been introduced in Southern France 

about ten years ago by Charabot and Laloue. We beg to point out that in the Barreme 

factory, erected by Schimmel S Co. in 1905, this well-known process has been made 

* us of in the distillation of lavender oil. 



^) Am&nc. Perfum. 16 (1921), 107. — *) We were hitherto anable to ascertain what is meant by Kasturi 
arsina. Probably, it is the case of Kasturi arishina ^= Curcuma aromatica, Salisb., or Kasturi- hhendi = Hibiscus 
Abelmoschus, L. (Cf. Dymock, Warden, and Hooper, Pfiannacographia Indicaj 1S90.) — *) French Pat. 505085, 
Oct. 1, 1920.. — *) Cf. Giidcmeister and Hoffijiann^ The Volatile Oils, 2"«* ed., vol. I, p. 247. — •) French 
Pat. 518713, May 30, 1921. As per Ch&m. ZmtraWl. 1921, IV. 596. — •) Perfum. Record 12(1921), 143; Chemist 
and Druggist U (1^21), 855. 



\ 



\ 



108 Report op Schimmel Si Co. 1922. 

In the same article, a second process, devised by Gattefoss6, is described tor re- 
covering essential oils from the distillation waters. The aqueous distillate passes in a 
very fine spray a layer of rectified petroleum in a closed vessel about ane-third full. 
The water is fed from above, gives off Its oil content to the hydrocarbon, separates at 
the bottom of the vessel and is siphoned off. This washing process is repeated several 
times. The oil obtained after evaporating the solvent is not nearly of the same quality 
as the oil resulting from direct distillation. 

Another process for recovering the essential oils suspected in the distillation 
waters has been patented by ). Amic, L. Roure, J. Roure, and P. Magiapan*). The 
water being separated from the oil in a receiver is conducted to the upper part of a 
distillation-column filled with coke pieces where it meets the vapours ascending from 
the still. The condensed liquid is siphoned off, while the vapours leaving the column 
are cooled in a condenser and then conducted to the receiver for separation. 

As to the "water oils" of various plants, we refer to pp. 48, 50, 58 and 59 of this Seport. 

Essential oils showing a tendency to resinify and to acquire a turpentiny odour 
are said to keep for an infinite time after adding for each 500 gr. of oil 3 gr. of sodium 
hydrogen sulphite '). 

In France, a patent has been granted to Lautler Fils') for a process of manufacturing 
pomades whereby the "chSssis" an prepared mechanically for the enfleurage process, 
i. e., coated with fat and fed with flowers. The latter drop automatically from a hopper 
on the greased "chassis" which pass the hopper on an endless belt. 

H. Schclenz*) furnished a small contribution towards the hintory of odoriferous 
and Mlet prqmratwns. Mankind has made use of these articles, more especially of 
the odorous drugs, from the very beginning. The Bible already mentions these pre- 
parations, without, however, giving credit in this respect to the achievements of the 
ancient Indians, Persians, and ^yptians. In the course of time, one got acquainted 
with the methods for obtaining the pure odoriferous substances and how to modify 
the original ways of using them. The scented powders, bags, pomades and sticks 
were substituted by products of distillation, either the essential oils proper, or to their 
' alcoholic solutions. In the 13<'' century, for instance, we hear of a "Hungarian Water" 
rosemary water) which was distilled from the strong-smelling rosemary at first with 
water, later on with wine. The dispensaries of the Italian, later on also of the French 
and German monasteries, where the volatile ails were distilled already in the iHiddle 
Ages, acquired in the course of time a high standing. In the IS"' century, the Carmelites 
traded an "Eau des Carmee" essentially an aqueous distillate of balm (meiissa) used 
for medicinal purposes, and some time after, the Italians made known in Cologne the 
Acgua della Begina, or "Eau de Cologne". This preparation is, in Schelenz' opinion, the 
earliest specimen of an alcoholic solution of essential oils. 

Bibliography. 

In Ullmann's "En!ykltq>ddie der technkcken Chemie", vol. IX (1921), the odoriferous 
bodies ("Biechstoffe"), are fully dealt with. The compilers, A. Hesse, A, Etlmer, and 
R. Haarmann, after giving a short historical introduction (starting from the fundamental 



Notes on scientific research. 109 

work of Tiemann and of Wallach and furnishing a review of the recent development 
of the technology of the aromaticsV deal with the process for preparing odoriferous 
substances and give furthermore a description of the complex aromatics, their con- 
stituents, and how the simple and the complex aromatics are obtained artificially. In 
the chapter ^'Allgemeine Methoden zur Geivinnung der. Riechstoffe" (General methods 
for preparing odoriferous substances), Hesse enters with particular interest into the 
distillation of otto of rose in Bulgaria, with which process he is acquainted owing 
to persona] inspection. He describes, inter alia, a duplex still for distilling roses 
(illustration) furnished by Egrot, of Paris, which shows some handsome and practical 
details^ just like the most of French machinery, but on the other hand, exhibits several 
serious drawbacks. Various contrivances, e.g., the badly^constructed still-head, show 
clearly that the French, unlike the German manufacturers, have not taken the trouble 
to study from a scientific standpoint the process of the steam-distillation or the water- 
distillation of plants. — In the chapter dealing with the natural complex odoriferous 
bodies, the more important essential oils, a well as various aromatics of vegetable or 
animal origin, their hitherto known components, and the analytical methods serving 
for the examination of these products are enumerated. — The components of essential 
oils, insofar as the occur as separate trade articles in the industry of aromatics, have 
been treated in detail by the authors. For instance, the numerous processes for 
obtaining vanillin, either from the natural products, or by synthesis, are fully dealt 
w;ith. — In the last chapter, "Zttw^iZic/ie Darstdlung, dnfacher und komplexer Riechstoffe" 
(Artificial preparation of simple and composed aromatics), the authors demonstrate, by 
various instances, how nearly all the ingredients of natural perfumes can be obtained 
by chemical means. In addition, many works processes for synthesising these products 
are communicated. A short compilation of statistical figures illustrating the German 
import and export of essential oils and aromatics during the last decades and showing 
the rapid evolution of the German "i^iecMojf" industry prior to the War, forms the last 
chapter of this treatise which is equally will furnished with illustrations and literary notes. 

Towards -the end of the 19*^ and the beginning of the 20*^ century, the cultivation 
of medicinal plants in Germany, as well as in other European countries, such as 
Holland, had gone do^n seriously. Since the beginning of the Great War, however 
more especially in the last years, a change has taken place, to which we referred 
repeatedly*). It was a necessity and an act of material self-respect to cover the demand 
for medicinal plants from home-grown products. People started again, more especially 
in Central and Southern Germany, to collect and cultivate drugs on a larger scale. 
These endeavours were aided by numerous societies, e.g., the ''Committee for propagating 
the collection and cultivation of medicinal and economical plants by Government 
measures^ ^ (Ausschufi zur staatlichen Forderung der Sammlung und des Anhaus arzneUich, 
wirtschaftlich und technisch verwertbarer Ffianzen) at Dresden, the "Hortus-Society" and 
the ^'Society for the promotion of the cultivation and collection of medicinal and 
aromatic plants" (Gesellschaft zur Forderung des Sammelns und des Anhaus von Gewurz- 
pflanzen) in Bavaria, and by the German Pharmaceutical Association (Deutsche Fharma- 
zeutische Gesellschaft) of Berlin. However, these endeavours and suffered opposition 
from various quarters. One of the objections made seemed to be somewhat justified 
insofar that it was considered unwise to enlarge the area used for drug cultivation 
in stead of cultivation of victuals and fodder, or of important vegetable raw-materials 



1) Cf. B&poHs 1917, 110; 1918, 78. 



110 Report of Schimmel § Co. 1922. 

fbr industrial purposes. The question arose, Is it commendable from an economic ' 
standpoint or not to increase the cultivation of tnedicinal plants in Germany. 

Th. Sabalitschka*), in an investigation entering very closely into this question, 
comes to the certain conclusion that in Germany the cultivation of medicinal herbs 
is in any case a serious necessity which, provided the proper herbs are selected. Is 
particularly provitable for small growers. After dealing with the cultivation of drugs 
in Antiquity and the Middle Ages, Sabalitschka enters upon the following points: — 
n. consumption in Germany, prior to the War and in future, of drugs obtainable in 
the country itself; h, drug imports into Germany prior to the War; c. profitableness 
(from the producer's view) of drug cultivation! d. advantages of cultivating drags for 
Germany's trade in general; ^- directions how to cultivate succesfully medicinal and 
aromatic herbs in Germany; /. cultivation of drugs in states other than Germany, and 
acknowledgement of the necessity of promoting the cultivation. 

Since Sabatitschka's paper touches but lightly our own domain, we content ourselves 
with the abo^ve review. In any case, we recommend sincerely the perusal of this extensive 
paper which is well supplemented, with statistical data on drug imports and exports. 

In addition to several short bulletins (in the manner of the Circulars of the Oe- 
partement of Agriculture, U. S. A.), the Italian "Federazione pro Montibus" has puUishpd ') 
a dictumary giving the vernacular names of the Italian medicinal and aromatic plants 
and the corresponding Latin terms. 

K. Bournot') gives a reiietc for 1920 of the research work on terpenes and essential oils. 

Analytical Notes. 

K. Hoepner*) deals with the various methods for estimating the alcakd content in 
presence of volatile substances. He discusses six methods worked out by the German 
Alcohol Monopoly Office for determining the free alcohol, not combined with acids, ' 
in mixtures of spirit with neutral volatile bodies (perfumes, hair tonics, mouth washs, 
mixtures of alcohol and esters, with exception of methyl alcohol an* of so-called 
fusel ail) and compares the results with his own experiments. Two of these methods, 
a) diluting and salting out the sample, then distilling and taking the specific gravity 
ol the distillate, b) chromic aiiid process without previous skaking out with sodium 
sulphate and light petroleum, proved to be unreliable and should be abandoned. 
Equally the method consisting of diluting with salt solution, then shaking out with 
light petroleum and distilling the spirit, cannot be recommended. Of the remaining 
three processes the one consisting of calculating the alcohol content direct from the 
specific gravity is applJable only in cases when the composition of the preparation 
is known as to the density and quantity of the dilute alcohol and of the dilute volatile 
constituent; in addition, a table for calculating the actual alcohol strength must be 
consulted. The method basing on the process of diluting and shaking out with light 
petroleum of the neutral volatile Ingredients, where the alcohol present is calculated 
from the density of the distillate, furnishes values which are in the most cases too 





,„l^ta«J, ^ .«W B.nt.Uiitm ««d «,«. Fsrt«fe 








a copy kindly lorwardid to us. — ^ Domenico 








- ■) CT™, .Sd- 46 (1921), 531. - ■) &ii,chr. 







Notes on scientific research. , tit 

low^ anyhow the errors can be eliminated to some extent by certain manipulations. 
The freqlient emulsions occurring here are a great drawback. Satisfactory results are 
obtained by the following chromic acid process: — dilute with sodium sulphate solution, 
extract with light petroleum, oxidise the alcohol with potassium bichromate and sul- 
phuric acid to acetic acid, calculate the alcohol present from the amount of bichromate 
consumed — but only if the portions of water-solqble esters remaining in the sulphate 
solution are duly taken in consideration, as well as the increase in volume caused 
by solution of the volatile components. For carrying out this bichromate ^pfocess, 
small quantities, say 5 ccm., are sufficient 

The author finally gives the following improved directions for estimating the 
alcohol contained In alcoholic preparations together with volatile substances a) by 
means of the specific gravity, b) by the chromic acid process: — 

ay 50 gr. of the sample, which must be free from glycerin, resins, or other extract substances, are 
given into a separating funnel, 50 gr. water then added, finally 50 cc. light petroleum ("petroleum benzine") 
and shaken vigorously several times. The next day, the lower layer is given into a tared flask and brought 
to 99 gr. The alcohol content as calculated from the density must be multiplied by 2. Special directions 
are given for removing glycerin, resin, or free acids before carrying ont the estimation, in case these bodies 
should be present. 

&) 25 or 50 cc. of the sample (according to the preliminary alcohol content as calculated from the 
density) are given into a tared flask containing about 25 cc. of water, then weighed and diluted up to 500 cc. 
with a 12.5 per cent, solution of sodium sulphate. The mixture is shaken repeatedly and vigorously with 
petroleum benzine, the sulphate solution drawn off when fully clear and shaken with fresh 50 cc. petroleum 
benzine. The next day. 10 cc. of the fully clear sulphate solution are mixed with 25 ccm. 2N-potassium bi« 
chromate solution and 50 cc. dilute sulphuric acid and cooled down under the tap. After a lapse of two or 
three hours, the mixture is transferred into a 500 cc. measuring flask and water is added up to the mark. 
Of this solution, 50cc.'are mixed with 20 cc. potassium iodide solution, then diluted, after 10 to 15 minutes 
with about 100 cc. water and titrated balk with decinormal sodium hyposulphite solution, using starch solution 
&s indicator. — In order to ascertain whether the sodium sulphate solution used for the oxidation still contains 
a small amount of water-soluble esters, 200 cc* of the sulphate solution are mixed with 10 cc. standard alkali 
solutioni and the next (lay the amount of alkali not required for saponifying the esters possibly present is 
titrated I back with standard acid. An amount of 0.2 cc. alkali is not considered. — Each cc. decinormal bi- 
chromate or hyposulphite solution «=» 0.0011512 gr. alcohol. — Glycerin, resms/ free acids or bases are removed* 
before carrying out the examination, as stated above. 

V/. 01czew?ki^) gives the following directions for estimating the alcohol content 
in essences: — 25 gr. of the liquid under examination, 25 gr. saturated salt solution, 
and 20 gr, petroleum ether (b. p. not exceeding 60*^) are given into a separating funnel, 
shaken thoroughly and as soon as the liquid is clear the lower layer is drawn off 
into a 300 cc. flask. The residual petroleum . ether is shaken once more with 15 cc. 
salt solution, the aqueous layer is given into the flask and, the contents, after adding 
some magnesium carbonate and debris of porous plate, are distilled into a pyknometer 
of 50 cc. capacity. 

When liquids show a strong tendency to emulsify with petroleum ether, or are 
rich in essential oil, double distillation is resorted to. From 25 gr. of the preparation 
and 50 gr. water, with addition of some alkali about 50 cc. are distilled (in case of 
foaming, the alkali is omitted, and tannin is added) directly into a separating funnel, 
the distillate is saturated with salt, then shaken out with 25 cc. petroleum ether, drawn 
off into a 300 cc. flask (the petroleum ether is likewise shaken out once again with 
salt solution), and the united aqueous liquids are again distilled, as in the first- 
mentioned process, into a pyknometer of 50 cc. capacity. 

The methods published hitherto for the detection of alcohol in essential oils are 
discussed by Utz*). We abstain from mentioning them here, since the author likewise 
has found them to be more or less unreliable. The process described in Gildemeister's 



») Pharm. Zmtralh. 62 (1921), 288. — «) Deutsche Parf. Ztg, 7 (1921), 217. 



112 Report of Schimmel ft Co. 1922. 

textbook') serves best for qualitative tests <fonnation of iodofomi) and for approximate 
quantitative determinations (shaking put a fairly large portion with water Pr salt solution). 

The process devised by Verley and Boelsing*) for the quantitative estimation of 
akohoh and phenols (more especially of santalol, menthol, and eugenol) has been ■ 
re-examined by H. W. van Urk"). The result was this that none of the substances 
mentioned above can be estimated accurately by that method. Since years ago we 
entered fully into the details of the process and found it to be unreliable') we con- 
sider^ it unnecessary to occupy ourselves furthermore with van Urk's publication. 

In order to determine the amount of phenols in essential oils the method devised 
first by Gildemeister*) for testing thyme oil and improved later on by us°) has, in 
general, proved satisfactory; it consists in shaking 10 cc. oil in a cassia flask of fully 
too cc. capacity with a caustic soda solution of 3 or 5 per cent., and calculating the 
phenol content from the amount of tiie oil dissolved in the lye. W. H. Simmons') 
proved by way of experiment, that with thyme and cinnamon leaf oils 5 cc. oil on 
treatment with a 5 per cent, caustic potash lye, give a distinctly higher proportion of 
phenols than when 10 cc. of the oils are employed. Hitherto, the author was unable 
to prove with certainty whether the lower or the higher values were the correct ones. 
Comparative tests with clove, bay, and pimento oils gave the same results with 5 or 
10 cc. oil. (On the whole, too strong lyes give too high results, since the lye, in 
' connection with the phenol alkali, dissolves also part of the non-phenols. For this 
reason, we shake some oils, «.' g., clove oil, with a caustic solution of but 3 per cent.) 

With the object to determine the composition of mixtures of eugenol and iso- 
eugenol, in the preparation of vanillin from eugenol, P. V. McKie') constructed a curve 
illustrating the melting points of mixtures of pure eugenol and pure tsoeugenol ben- 
zoates, m. p. 69.5 and 104° respectively, following the method described in a previous 
paper"), A well-marked eutectic point was observed at a temperature of 56.5°, 
corresponding with a composition of 25.5 per cent, of i^oeugendl benzoate. Although 
at temperatures from 83 to 86°, and at compositions approximating to the equimolar 
mixture, the curve showed a discontinuity, the use of the melting point as a means 
of determining the composition of mixtures is thereby not invalidated. 

The authoress obtained the esters by dissolving the crude oil, resulting from the 
isomerisation of eugenol, in pyridine, and treating with some 25 per cent, excess of 
benzoyl chloride. The major portion of the benzoates separates as a solid, and a 
further quantity on pouring the pyridine solution into dilute sulphuric acid. The 
resulting benzoates were dissolved in ether, from which, on evaporation of the ether, 
the solid benzoate mixture is obtained. 

When, years ago'"), we estimated citrondiol according to the formylation method, 
we found that part of the alcohol undergoes a change. In order to elucidate this 
reaction, A. St. Pfau") formylated each 100 gr. ot citronellol (b. p. 105° [73 mm.], 
6 months' old preparation) by boiling for one hour with each 200 cc. of 100 per cent 
and of 85 per cent, formic acid. The formylation products (ester v. 295.4 ^ 96.4 per cent., 

>) GiLdcmeister and Hoffmann, The V'Aatile Oita. Z" ed., vol. I. p. 612. — ') Cf. S^pori April 1902, 25. 
— •) Pharm. Wtekblad 68 (1921), 1265. As per Ohem. ZentratU. 19SI, IV. 1145. — ■) Cf. BepoH April 1808, 
27. — ') Hager, Fischer and Hartwich, Eommentar rum ArmeiliwJi f d. Ihvti'^ Btich, s. Auag. Berlin 188B, 
!•' ed., vol. I, p. 377. — ") ScjMirt April 11X17/ 119, — ') Per^m. Keconi li (1921), 394, — ') Janm. dtan. 
S.«, 119 (1921), 777. — ■) J(nd, 111 (1918), 799, — •'} Ct lUpurl October nis, b*. — ") Jo..™,/: j-.«*t. 
Chim. y. F. Ite (1921), 276. 



Notes ON SCIENTIFIC RESEARCH. 113 

\ ' ■ 

I 

and 263.0 = 84.3 per pent, citronellol) were separated into 6 and 5 fractions respec- 
tively. It was then found that there had been formed on the average, in formylation : — 

With the With the' 

100 per cent, acid 85 per cent, acid 

Terpenes and citronellol .... 1 per cent. 3 per cent, 

Citronellyl formiate ..... 20 „ „ 30 „ „ 

Citronellyl glycol monoformiate^) 35 „ „ 40 „ „ 

Citronellyl glycol diformiate®) . 29 „ „ 12 „ „ 

Residue, polymerized 15 „ „ 15 „ „ 

By the same treatment, citronellyl formiate gave rise to a product of the following 
composition: — Unchanged citronellyl formiate, 35 per cent.; citronellyl glycol di- 
formiate, 50 per cent; polymerized residue, 15 per cent. 

Hence the exceedingly high values obtained by determining pure citronellol by 
the formylation method^), are due to the formation of citronellyl glycol diformiate. 

Pfau concludes, as result of his work, that the formylation process for estimating 
citronellol furnishes irregular values and affords no clue as to the true content of 
citronellol. This is nothing novel, as we always have pointed out*) that this process 
is not an exact one, although it may be satisfactory in practical work. 

Equally, C. T. Bennett*) tested the formylation method by varying the conditions 
and came to the conclusion that the method is unreliable for the determination either 
of citronellol or citronellal. 

With regard to these two articles by Pfau and Bennett, W. H, Simmons^) is of 
opinion that both workers confirpi his own conclusions on the subject, but apparently 
ignore what he considered to be most important, viz.y that the method is a very useful one 
for comparing the relative proportions of citronellol in different geranium oils, as was 
suggested by him in 1913. Subsequent experience with a very large number of samples 
of African and Bourbon geranium oils fully confirmed the view which Simmons then 
expressed. It is very important to adhere strictly to one and the same direction and 
to heat for exactly 60 minutes on a boiling water bath, and not on a sand bath. 

For the estimation of terpin hydrate in elixir of terpin hydrate Nat. Form."^), 
A. G. Murray®) gives the following directions:— The elixir is mixed with a solution 
of 20 gr. comijnon salt in 100 ccm. of water until the alcohol content is from 10 to 
15 per cent, by volume. The mixture is shaken out with four portions, one-fourth 
volume each, of chloroform containing 5 to 7 per cent, by volume alcohol. Each 
portion of the solvent is washed successively with 5 ccm. salt solution, then filtered 
into a tared beaker, and evaporated by aid of a blast, avoiding application of heat. 
(On evaporating an alcoholic solution of terpin on the water bath, about 10 per cent, 
of the terpin hydrate were found to volatilize.) The residual pure terpin hydrate is 
dried at the open air and then weighed. The error was only +0.8 per cent. 

The acetylation of both hydroxyl groups in terpin may be carried out by boiling the 
glycol for three hours with eight times its weight of acetic acid and five times its weight 



^) di50 0.9651; ao+l^Ab'; noi50 1.4488. — «) diB© 0.9976; ao + l°33'; noiso 1.4425. — *) Ct Report 
October 1918, 64. — *) Gildemeister and Hoffmann, The Volatile Oils, 2"<* ed., vol. I, p. 600. — ») Per/um, 
Secord 12 (1921), 351. — «) Ibidem 398. — "O It contains, in addition to about 1 grain (0.175 gr.) of terpin 
hydrate, tincture of sweet orange peel, spirit of bitter almond, alcohol, glycerin, and syrup in 1 fl. dr. — 
*) Joum. Amer. pharm. Ass. 10 (1921), 440. 

8 



114 



Report of Schimmel S Co. 1922. 



of a neutral solvent, «. g.^ turpentine oil, with addition of sodium acetate. Basing on this 
reaction O. Fernandez and N. Luengo^) worked out a method for the estimation of terpin. 

Although the inapcuracy of the phosphoric acid process for tht determination of 
cineole is long known — even C. E. Sage and'J. D. Kettle*) admit readily that the method 
is not so exact as a purely chemical method — we very frequently meet with endeavours 
to puff up that process whenever an opportunity arises. Such an opportunity arose 
recently with the publication of lusting Cooking's cresineol method') and Weber's and 
von Rechenberg's*) solidification point test. Sage and Kettle point out that the former 
author*), when comparing the "phosphoric" and "resorcinol" methods, found considerable 
discrepancy between the results of both methods (which fact we take as proof for the 
inaccuracy of the "phosphoric" method), and now they publish the results of compar- 
ative cineole determinations in a few eucalyptus oils and cineole samples, carried out 
according to the "phosphoric", cresineol, and solidification point methods. The results 
which differ to the utmost by 6 per cent, and are hardly worth any discussion, are, in 
our opinion, not in favour of the phosphoric acid process, as the authors maintain. 



F. B. Power*) recommends the following process for detecting methyl 
anthranilate in fruit juices: — From. 500 ccm. of the liquid 200 ccm. are 
distilled off, and the distillate which in presence of an appreciable 
quantity of the ester shows a bluish fluorescence, is shaken out three 
. times with each 10 ccm. of chloroform {not ether). The residue ob- 
tained on careful evaporation of the chloroform extract is immediately 
treated with 2 ccm. of 10 per cent sulphuric acid, the acid liquor is 
transferred to a test-tube and cooled. To the liquor one drop of a 5 
per cent, solution of sodium nitrite is added, then a few crystals of 
urea, and subsequently one of the following two reagents: — a. a mixture 
of one ccm, of a 0,5 per cent, solution of pure /^-naphthol containing 
0.2 per cent, of sodium hydroxide, one ccm. of a 10 per cent, solution 
of sodium hydroxide, and one ccm. of a 10 per cent, solution of mono- 
hydrated sodium carbonate, Na2C08 • H2O. If not less than 0.0001 gr. 
of -methyl anthranilate is present, a yellowish-red precipitate will be 
produced; b. one drop of dimethylaniline, and, when the latter has 
completely dissolved, a slight excess of a 10 per cent, solution of sodium 
hydroxide. The 'yellowish coloration produced in presence of not less 
than 0.001 gr. of the ester changes to red on slightly acidifying the 
mixture with dilute sulphuric acid. 

By this process the author believes to have overcome the errors such 
as possible with the Erdmann method^) (incomplete separation of the ester 
which is not free from foreign admixtures). The results of the investigation 
of grape juices by this process are reserved for a future communication. 

The estimation of phenylacetaldehyde in the cassia flask according to 
the bisulphite method is often connected with difficulties and is frequently 
inexact, since the heavy non-aldehydic (polymerized) constituents of the aldehyde remain 
at the bottom of the flask. A. Reclaire®) recommends to modify the process as follows: — 




») Ann. 8OC. espanola Fis. Quim. [2] 18 (1920), 158. As per Chem. Zentralhl. 1921, IV. 687, — «) Perfunt, 
iiecord 12 (N21), 44. — ») Cf. ^mc/iMGcrman) 1921, 65. — *) J&trfem 35. — •) Cf. £epor< October 1910, 
67. _ 6) joum. Amer. chem. Soc. 43 (1921), 377. — ') Berl. Ber. 35 (1902), 24 and 2355. — •) Perfum. 
Becord 12 (1921), 341. 



Notes ON SCIENTIFIC RESEARCH. 115 

5 ccm. of phenylacetaldehyde are introduced into a 100 ccm. flask of special construction, 
then 20 to 25 ccm. of solution of sodium bisulphite (containing about 30 percent. NaHSO«); , 
the mixture is shaken vigorously for some minutes, and the whole is placed in a 
water-bath. After some time, boiling >%«iter is gradually a^ded until the solid compound 
at first produced is completely dissolved. More water is then added, and the non- 
aldehydes settle down in the graduated tube, where the volume can be read off wheti cold. 

As to the identification of nitrobenzene when present in bitter almond oil, see p. 6 
of this Report. 

Re the estimation of vanillin according to Doherty see p. 100 of this Report, 

% 

Physical Notes. 

As is generally known, the reason why the vapour tension curves of two sub- 
stances do not run parallel to each other is to be found in the difference of the 
changes of tension, with identical changes of the temperature. The numerous curves 
compiled by C. von Rechenberg ^) show that about 2000 pairs of curves cross each 
other. When, in agreement with v. Rechenberg, the. liquid and solid states are con- 
sidered as chemical formations which on heating are decomposed into vapour mole- 
cules, then the different stability of the molecular complexes is- the cause of the varying 
evolution of vapour,- hence the latter is a measure for the former. When working out 
the entire material v. Rechenberg was able to classify all the substances investigated 
in relation to the increase in vapour pressure for the equal rise in temperature, and 
this classification was clearly in accord with Rothmund's*) solubility series. It may, 
therefore, be concluded that in both cases the regularity is a result of the identical 
cause mentioned above. 

Furthermore, C. von Rechenberg') utilized his excellent material of vapour tension 
Curves for testing Bancroft's rule which implies that all mutually soiubje liquids of 
which the vapour tension curves cross each other form "distinguished" mixtures with 
either a minimum or maximum boiling point, v. Rechenberg was able to confirm the 
general applicability of that rule, but with the restriction that such mixtures with 
''distinguished" boiling points are limited to a certain range of pressure. 

With the object to investigate in the laboratory the separation of binary mixtures 
by continuous distillation, A. F. Dufton^) constructed a continuous still with a still-head 
as had been devised by S. F. Dufton*). The mixture to be separated was fed from a 
small flask, where it was electrically pre-heated to its boiling point, into the middle 
of the column. A siphon kept the level in the preheater constant. The lower part 
of the still was also heated electrically by a wire coil and the current required was 
measured by a watt^meter. To obviate any loss of heat from the lower part of the 
column, a thick lagging of cotton-wool surrounded by a steam-jacket was employed. 
":xact thermometers at the top of the still-head and at the bottom of the column 
ndicated the purity of the separating products. 

Starting from a 50 per cent, mixture of benzene and toluene the author succeeded 
1 regulating the still to work automatically, yielding pure benzene and pure toluene 
ontinuously. By measuring the head supply it was found that the separation of one 



1) Zettachr. f. physik. Chem. 99 (1921), 87. — «) Ibidem 26 (1898), 489. — ») lUdem 99 (1921), 105. — 
Joum. chem. Soc. 119 (1921)^ 1988. — ») Jotirn. Soc. chem. Industry 88 (1919), 38 T; Binicht (German) 1920, 101. 

8* 






11,6 Report OF ScHiMMEL a Co. 1922. 

gram of benzene required 1340 calories. As the theoretical quantity of heat required 
is calculated to be 208 calories*) the- thermal efficiency of the still was 15.5 percent. 
When other still-heads were employed, for instance copper gauze discs, or thin- 
walled cylindrical glass beads, 4 mm. long and^ mm. in diameter, the thermal effici- 
ency*), with a 50 per cent, mixture of both hydrocarbons, was up to 47 per cent. 

L. Smith ^) publishes some laboratory notes on the efficiency of still-heads in 
vacuum distillation. We , agree with the author that the circumstances, in vacuum 
distillation, are not fully comparable to those under atmospheric pressure; in the 
present case, however, the method employed for testing was ^not sufficiently sensitive, 
so that the values derived afforded no evidence towards the question which has been 
elaborately sftudied by other authors*). 

Years ago it has been demonstrated by A. Hantzsch*^ that it is possible to test 
the constitution as well as the parity of terpenes by means of the tdtraiviolet ray 
absorption. , A. Muller®) employed this method for examining citronellol, geraniol, and 
' their derivatives. As the author communicates, it is sufficient, it is true, for obtaining 
the pure alcohols and their acetates to make Use of the ordinary ' distillation process, 
whereas the purification of'the cylic alcohols and their esters is said to be difficult. 
Unfortunately though, he furnishes but insufficiently the constants of the preparatioihs 
under examination (the refractive index being nowhere recorded, and the optical rotation 
only in part) from which the purity of the preparations might have been judged. The 
solutions were prepared by means of optically pure alcohol. A citronellol obtained 
from Java citronella oil (b. p. 112.5 at 8 mm., diso 0.861 i2, aDjoo 2^16'') showed stronger 
absorption than a citronellol obtained from citroneltal by reduction (b. p. 113.2^ at 8 mm., 
di6o 0,8600, onajo 4° 5'). A sample of geraniol (b^ p. 108.2° at 9 mm., di6o 0,8836) purified 
from its calcium chloride compound^) showed a still lower absorption, and that of 
reuniol. lay between that of citronellol and geraniol, but nearer towards the latter. 
With the acetates of the two alcohols the distance of the. absorption curves was even 
larger. With the cyclic alcohols (cyclisation was performed by treating the esters 
with phosphoric acid at low temperature) the absorption bands approached each other 
the closer, the more the esters were subjected to fractional distillation. The purest- 
preparations, cyc^o-citronellol (b.p. 97 to 101° at 8V« mm., di5o 0.9023, aD»o2O30'') 
and cyc^o-geraniol (b. p. 96 to '98° at 11 mm., diso 0.9462) showed but a feeble difference 
in the position of the absorption bands ; with the cyclic esters, however, the differences 
were greater. The hydrogenated alcohols: — dihydrocitronellol (b.p. 113.5P at 15mm*, 
di6o 0.8565) and tetrahydrogeraniol (b.p. 116 to 117.5° at 14.5 mm., dwo 0.8621), with 
which the bands were located more towards the ultraviolet part of the spectrum,, 
possessed nearly the identical absorption. Since likewise the results of the chemical ' 
examination indicated that in the hydrogenated alcohols the alkyl group occupied the 
same position, the alcohols proved to be ^ : ^-dimethyl octanol-S. 

With regard to earlier chemical investigation^), the author, basing on his optica] 
examination, arrives at the conclusion that reuniol is merely a mixture of citronellol 



») Joum. Soc. chem. Industry 38 (1919), 38 T; Bericht (German) 1920, 101. — ^) Phil. Mag. VI, 42 (1919), 
633. — «) Joum. f.prakt. Chem. II, 102 (1921), 295. — *) Cf. BeHcht (German) 1920, 101. — ») Cf. Report 
April 1912, 156. — «) Berl. Berichte 64 (1921), 1466. — ') The direction of the rotation is not stated. 
— ^) In a paper published in the Deutsche Parfiimeriezeitung dealing with the identical subject the author 
believes this calcium chloride compound to have been discovered in our laboratory. This is a mistake. This 
compound was first obtained by O. Jacobsen (Liehig^s Ann. 157 [1871], 234. — ») Cf. Gildemeister and Hoffmann, 
The Volatile Oils, 2"^ ed., vol. I, p. 364. Report October 1904, 119. 



Motes on sciemtific research, tl7 

and geraniol (with at least 60 per cent of geranJol), and that it must be struck off from 
chemical literature. 

The absorption power of ultraviolet rays by various phenols and phenol ethers 
has been studied by Th. fi. Durrans'). Jsoeugenol proved to absorb- ultraviolet rays 
. much more than eugenol, and by methylatlng a phenol hydroxyl, e. g.. in ut»eugenol, 
the absorption power for ultraviolet light is doubled. The absorption is likewise 
raised, in a Still higher degree, by introducing the allyl side-chain, whereas by the 
propenyl side-chain the power of absorbing ultraviolet light becomes very small, as 
was shown by comparison of anisole, anethole, and methyl chavicol. 

The irivestigatioh started by Rupe on the influence of the constitution on the 
i^tical rotation of active substances has been continued by A. Krethlow and K. Lang- 
bein"). In order to obtain further insight into the relation between rotatoiy dispersion 
and spectral absorption the authors examined such optically active substances as 
show marked or at least incipient, selective absorption of light in the neighbourhood 
of the visible spectrum as to their abnormal rotatory dispersion. Of 19 optically active 
bodies examined, six were perfectly normal in their optical behaviour, as they showed 
neither abnormal rotatory dispersion nor any selective absorption of light (amongst 
then camphorylidene-d;_acetic acid methyl ester and camphoryK^-acetic acid). Seven 
substances manifested anomalies in rotatory dispersion, amongst which were various 
menthyl esters,' e. g., of diacetoacetic and of pyruvic acids. .Benialcamphorylidene 
acetone and styrylbenzoylacetic acid menthyl ester behaved polanmetrically normal, 
but showed beginning spectral absorption. . , 

The authors deduct from their investigations that a parallelism between abnormal 
rotatory dispersion and selective spectral absorption does not appear to exist. Amongst 
33 bodies, only three (the white diphenylmethylacetoacetic and phenylbenzoyl acetic 
acid menthyl esters, besides the pale yellow diphenylmethylal camphor) were found 
which showed both anomality in the rotatory dispersion and selective absorption of tight'). 

F. Eisenlohr*) reports on the molecular refraction of higher-melting Bodies, and how 
the corresponding refractive indices are recalculated on the standard temperature of 20°. 

A. Muller') observed anisotr(^)ism in the melting point of dlanisalc^cJohexanone 

(prepared from pure cydohexiuione and anisic aldehyde). At 160 to 161°, the body 

liquefied into an opaque mass which clarified suddenly at I?!''.. The phenomenon of 

voluntary spreading- out on wate? in a very thin film (long known with oleic acid and 

other bodies) has been observed by A. Marcelin') with a series of other substances. 

The experiments were carried out in the following manner: — When a small piece of 

camphor is floated on water, the surface of which was sprinkled with talc powder, 

pne could observe how the talc grains were driven away from the camphor piece so 

that an emotv circle was formed round the latter. The diameter of this "halo" reached 

pending upon the equilibrium ruling between the velocity of the dissolving 

unphor layer formed, and of the re-formation from the camphor piece, 

hotographs of this process was taken. From the area of the circle and 

eight of the camphor piece the thickness of the layer was calculated. 

(below 3° C.) showed the same phenomenon when floating on water. 



1 



118 Report of Schimmel S Co. 1922. 

When repeating the experiment with water on which oleic acid had been spread 
out previously, a halo was likewise formed, the diameter of which allowed of comparing 
the relative surface tension. Hereby the following figures resulted: — dimethylpyrolidone, 
31.5; dimethyl campholic acid amide, 29.7; i^obutylbomeol (-camphol), 20,4; menthol, 
20.4; j}-toluidine, 16.7; camphor, 13; thymol, 12.1; borneol, 11.1; propylcamphocarbonic 

acid methyl ester, 9.4; benzal camphor, 0.94. 

* 

According to F. Hogewind*), nearly all odoriferous bodies, after long standing of 
their aqueous solution, show colloid properties. The odour was then found to be but 
slightly less intense than with the onginal oil ; in addition, a layer of pure water, 
when poured carefully on such a colloidal solution, was found to assume the odour 
of the aromatic in question. These phenomena are readily explained by the well-known 
fact that the bodies mentioned show more or less the tendency to polymerise and 
resinify partly. In this process products are always formed which are far less soluble, 
and which, owing to the low concentration of the initial solutions, yield stable hydrosols. 

A. Muller*) describes and recemmends an apparatus for determining the viscosity 
of essential oils termed "viscosostalagmometer*'. As years ago*) we established by 
way of experiment that the determination of this constant is of but little value when 
judging essential oils, we need not enter into a description of Muller^s apparatus, 
which in its main features differs but slightly from the viscosimeters devised by 
Arrhenius, Ubbelohde^, Engler, and others. 

Botanical Notes. 

Two hybrids of spike and lavender are described by M. Humbert*). 

Hybrid A, growing up to 1 m. height, resembles in general habit and appearance 
a strong L. lati/olia and is found here arid there, more or less isolated, in the north 
of St. Satumin-les-Apt at about 800 m. altitude, also near Buis-les-Baronnies about 
400 m. altitude, in the Nyonais, and in the Gausses. The flower stalks, divergent as in 
L. lati/olia, generally bear in the axils of two higher leaves a pair of secondary flowering 
branches. At the base of the bushy, more or less interrupted inflorescences, often 
exceeding 10 cm. in length, the pairs of lower leaves form false rosettes. The bracts, 
in whose axils 6 to 12 flowers stand, remain green a long time even after flowering, 
at least in their upper part. 

Hybrid B, whose height varies between 30 and 80 om., resembles more L. officinalis, 
is found in great abundance throughout the entire zone of contact between L, latifolia 
and L. officinalis, often as numerous as the parents. The flower stalks are more or 
less divergent, generally simple, but sometimes bear in the axils of two higher leaves 
a pair of secondary branches. The lower leaves, approaching the base of the flower- 
bearing branches, form false rosettes but not so distinct as in L. latifolia or in 
hybrid A. The bracts are brown and membraneous after flowering. The slender 
inflorescence is 1.5 to 6 cm. long, usually not interrupted; 1 to 5 flowers stand in 
the axil of each bract. 

The following characters are common to both hybrids : ~ 1 . The flowering begins 
later than in L. officinalis and earlier than in L, latifolia. 2. The seeds are almost always 
sterile. 3. On bruising the plant a camphoraceous odour is noticed. 



^) Archives neerland. de Physiol, de Vhomme et des animaux 5 (1920), 153. — ") Chem.-Ztg. 4& {\92\), 759.' 
— «) Cf. BepoH April 1901, 31. — *) Perfum. Record 12 (1921), 177. 






Notes on scientific research. 



119 






Two other hybrids, A' and B', from L. officinalis var. pyrenaica and L. latifolia, 
correspond to the hybrids A and B described above. The species B'^) resembling more 
L. pyrenaica and termed L. aurigenara*) differs from hybrid B by the large size of its 
bracts. The more frequent hybrid A' shows greatly developed bracteoles and an odour 
of camphor. Side by side with those hybrids there exist various other hybrid forms. 

R. Laubert*) gives a description of the most important diseases of aromatic plants, 
their origin and symptoms. Amongst the diseases known to occur with roses*), the 
much-dreaded white rose-blight takes the foremost place. It is caused by a fungus 
belonging to the Erysihacem, Sphcerotheca pannosa, (Wallr.) Lev. f. rosrs, and appears in 
shape of a white, dust- or flour-like deposit on the leaves, particularly on the tops 
of the young shoots. On the petioles and the calyces of the blossoms as well as on 
the fruits the white fur shows a coarse, fluffy appearance. Some rose varieties are 
attacked by this fungus but slightly, others are known to be very ready victims, e.g., 
the Crimson Rambler. — Another rose fungus, Phragmidium subcorticosum, (Schrank) 
Winter (N. O. Fucciniacece) is recognized Jby its bright orange-red, oblong or round, 
pulvinate weals occurring in spring on the leaves, their stalks, and on other green 
parts. In the course of the summer, there may be found on the back side of the 
leaves small, light orange-yellow dusty pustules, at first only a few, but growing in 
number^ which then turn black and sooty; on the upper side of the leaf, corresponding 
small yellow or reddish spots appear. Since the leaves attacked by this fungus turn 
yellow and fall off prematurely, the plants are seriously injured by this disease. The 
most of the high-class varieties known as remontant roses are readily attacked, in a 
less degree the tea hybrids and tea roses, whereas climbing and mountain roses are 
hardly ever afflicted. — The disease known as black spot blight (Sternrusstau) of the 
rose leaves occurs principally during damp weather and manifests itself on the upper 
side of the leaves in shape of round brownish-black or violet4>lack spots wbich on 
magnification prove to be composed of small dots and show a finely-radiated, fringed 
margin. The disease which likewise cauises the leaves to fall off prematurely is generated 
by a fungus sponging upon the green leaves, Actinonema i'osce, (Lib.) Fries (N. 0. 
Sphaerioidaceas), Low-growing roses are preferably attacked by this disease. — The 
Peronospora disease of the roses is, on the whole, not very common, but at times rather 
dangerous. It can be recognized by small spots on the leaves, which occur irregularly 
and sporadically and are in the beginning yellowish-grey, later on yellowish-brown. The 
disease occurs sometimes with roses cultivated under glass and with rose seedlings 
and is caused by the sponging fungus Peronospora sparsa, Berk. (N. O. Peronosporacece), 
Some rose gardeners consider the disease caused by a fungus named Coniothyrum 
Wernsdorffice Laubert*) (brown blight) to be the most dangerous of all rose diseases, 
since at times much damage is caused by this fungus. Early in spring, sporadic big 
round dark spots get visible on the green bark of the branches, particularly on the 
buds, which afterwards turn leather-brown to greyish-brown. Later on, the mortified 
bark splits up and peels off, whereby the woody interior gets visible. When the spot 



^) As per a paper by J. Gattefoss6 (Parfum. modeme 14 [1921], 207) this hybrid was found in 1877 in the 

enees by Father Sennen and was termed L. Senneni by Abb6 Coste. The hybrid L. aurigerana, Mailho, on 

other hand, shows more the character of X. latifolia and would correspond to the hybrid A. — *) In the 

\dex Kewenais, a species L. aurigerana, Mailho is enumerated. — *) Deutsche Parf. Ztg. 8 (1922X 1> 17. — 

Cf. Beport October 1916, 71. — *) The so-called Carcinoma rosce, recognizable by the abnormal extuberances, 

generated not by the fungus Coniothyrum Fuckeliiy but by lesions and action of the frost early in March. 

le fungus is but a secondary phenomenon. Cf. Sorauer, Handbucfi der Pflanzenkrankheiten, 1931, vol. I. p. 658. 



120 ^^ Report of SghimmelSCo. 1922. 

spreads round the branch the latter mortifies partly or totally. — The so-called Botrytis 
rot of the rose buds occurs in the summer when in the flowering, time the weather is 
cool and damp. The rose buds, instead of opening, do not develop further, change 
colour and get covered with an ash-grey coating of the fungus Botrytis dnerea, Pers. 
(N. 0. Mucedinaceos.) Under favourable growing-conditions the plant is, in the most 
cases, not liable to suffer seriously by this fungus. 

For combating these rose diseases the author recommends partly spraying with 
sulphurated substances, e. g., powdered sulphur, solutions of calcium or potassium 
sulphide, Sc, in case of Sphaerotheea pannosa, partly prophylactic treatment with sprays 
of copper preparations (copper-and-lime solution against Fhragmidmm, Actinonema, 
Peronosposa and other leaf fungi). Careful treatment of the roses, such as proper 
cutting and pruning, correct fertilization and tilling of the beds is likewise most essential. 

About 35 different fungi have been found on the various species of mint, but only 
a part of them are parasites or cause diseases. Of the noxious fungi, the following 
may be mentioned. Puccinia Menthoe, Pers. (N. O. Pucciniacece)^ the very common mint 
rust, occurs in two chief forms, the uredo-,or summer-spores, and the teleuto- or 
winter-spores. In summer time cinnamon-brown, wart-like, dusty pustules appear on 
the back side of the leaves, at first sporadically, afterwards in growing numbers, which 
constitute the stroma generating the unicellular summer (uredo) spores with pale yellow, 
short-bristled membrane. The uredospores communicate the disease in summer from 
leaf to leaf and from plant to plant. In addition to the brown pustules, largar black 
dust-like tubercles appear, the teleuto-stroma of the same fut^us. They generate the 
oval, bicellular winter spores with a brown, wart-like membrane and long colourless 
petioles. When these teleutospores germinate in the next spring and form sporidia 
which infect the mint, the second, less comjnon form of the disease develops in which 
the stalks and the petioles of the leaves acquire abnormal stoutness and are streaked 
by the n^ycelium of the rust fungus. The mint rust which occasionally causes deterioration 
of the odour of the plant and its oil, and often enough has destroyed the entire crop, 
is found not only on numerous species of Mentha^ but also on various other members 
of the family Labiatce (t. g., Calamintha, Clinopodium, Origanum, SatureiaJ. However^ 
not all the species an infected equally often or in an equal degree. For instance, 
Mentha arvensis Is attacked by one of the eight different varieties of Puccinia Mentkm 
which does not or but slightly attack other species of Mentha. These biological properties 
must be considered when combating the rust disease. By raising the miht plantations 
in suitable uninfected soil the appearing of the disease can be warded off or at least 
its spreading can be limited. 

Another disease, the so-called mint mildew, has been observed occasionally on 
Mentha arvensis. The green parts of the plants get covered with a white, flour-like 
coating which originates from an Erysibacea, Erysiphe Galeopsidis, D. C, or E. Cicho- 
racearum, D. C. — The fungus Septoria Menthce, (Thurm) Oud. causes the septoria spotted- 
leaf-disease of the mints which appears on the leaves of Mentha arvensis and perhaps 
also of other species in shape of black-lined, dark, later on light-grey spots. The mint 
septoria seems to be of minor importance. The same holds good for the following three 
diseases: — The ramularia spotted-leaf-disease (caused by Bamularia menthicola, Sacc. 
[Mucedinaceos]) on the leaves of M. sUvestris, M. aquatica, M. canadensis, M. arvensis; 
the physoderma weal disease of mints (caused by Physodenna Menthce, Schroet. 
[Cladochytriacece] and characterized by blackish-brown callosities on the stalks and 
leaves of Mentha aquatica)^ and the synchytrium papillary disease of mints (caused by 
Synchytrium aureum, Schroet. [SynchytriaceceJ), golden-yellow nodules on the stalks and 



Motes om scientific research, 121 

(eaves of Mentha aquatica. The fusarium stalk rot, caused by the mycehum of Pttsarium 
I^ntki, Prid et Elel. and J", rosetan, Meng. (Tubercyiariacea) , which occurs occasionally 
in mint plantations is not quite as hannless as the preceding fungi. In this disease, 
the stalks turn blackish-brown at the base and wither. The following measures arc 
recommended against this disease: — Destroying of all infected plants, suspendfng the 
cultivation of mints for several years, and, if necessary, disinfecting the soil, 

Phytophyslologlcal Motes. 

With the object of studying the process of formation, in the plant, of the essential 
oU, |, Politis') investigated the secretory hairs of various labiata and geraniaces. In 
the secretory cells of the hairs, during the first stage of their formation, numerous 
oblong and twisted "chondriocontes"') are observable which contain a tannin com- 
pound. These "chondriocontes" widen gradually at each of their ends aiid separate 
thus that both from each a separate globule. These globules increase in size and pass 
over into the vacuoles of the cell Where in course of time they are dissolved by the 
vacuole liquid. The content of the vacuole then shows feeble refractory power, and 
instead of the disappearing tannin, essential oil is formed^), 

E. Canals') investigated the influence exercised by rays of varying wai'e-lengths 
on the formation of essential oil in the plant. For this reason, the author transplanted 
young thyme plants grown in uncultivated land into pots and arranged them in boxes 
beneath ordinary (1), blue (2), or red (3) glass panes. After lapse of 20 days, all the 
plants in box (1) were in bloom, but showed pale blossoms, long stalks, and light green 
leaves. The plants in box (2) were like the former, some of them had faded away. In 
box (3), but a very lew plants had attained a poorly blossoming stage, their stalks were 
excessive long and Che leaves very broad. The thyme plants had entirely lost tiieir 
xerophilous character. The oils distilled from the various plants showed the following 
percentage of thymol: — 

Plants in box 3 (red glass) , . , 25.5 per cent, thymol 

2 (blue glass) ... 36 „ 

„ I (ordinary glass) . 45 „ „ 

„ from open air 52 „ „ „ 

From these observations the author concludes that the thymol content of the oil 
decreases to the same extent as the plant loses its xerophilous character, and that the 
chemically active blue rays exercise an unfavourable influence on the formation of 
thymol which is tar more marked with the calorific red rays. 

. The result of this study is in accord with earlier investigations and might have 
been expected. According to Lubimenko and rSovikofC), light is indispensable in the 
formation of essential oil in the plant, but increased etiolation, at least within certain 
limits, raises the yield of oil. On the other hand"), in most cases the rays of high 



be lound in (he Jilerature al our diiposal. With 'chondres" various species o( granules are designed which 
occur In the nucleus and fomi the connections between the Uyuc in the fratne, — *) Alteady years ago, various 
■cientlits, eg. Hedtel and SchlagdenhauHen {Ompt. rmd. 114 [IS92], 1291) tavoured the theory that there exists 
some connection between the lormafion of essential oil in the plant and the tannins. — ') Bull, floure Bertrand 
PtIs. April 1B21, S. — >) ^11. (ifiplt&i Bql. 7 (I9U), M7. M pa not.ZeHtmat. lift (I9\5), ffib. The abatract 
on ba^l oil published in The Amcr. Perfitmrr 10 (I91&), 265, without mentioning the source, pertains to this 
paper by Lubimenko and Movikoff which we dealt wiih in our Rtport IQie, 5. — •) Pretler, Pffanim- 
fihyaiulagie, 2" ed. vol. 11, p. 117. 



122 Report of Schimmel S Co. 1922. 

refraction (blue to ultraviolet) exercise the same influence on the plant development 
as does weakened mixed light, while red and yellow light causes the s^me alterations 
in the plant as continuous darkness. 

The emulsin obtained by aqueous maceration of almonds and precipitation of the 
extract with alcohol is a mixture of various enzymes containing, in addition to /9-gluco- 
sidase (emulsin proper), lactase, gentiobiase, invertase, cellobiase, i^-galactosidase, and 
other ferments. According to M. Bridel and R. Arnold*) it makes no difference in the 
preparation of emulsin whether ethyl alcohol, methyl alcohol, or acetone is employed. 
However, by varying the time during which the precipitant is allowed to act on the 
precipitate, emulsin preparations may be obtained in which soiifie of the enzymes 
mentioned^ e.g., lactase or invertase, are missing. 

Physiological and pharmacological Notes. 

In an elaborate paper entitled. Die Biechstoffe und das Riechen (On aromatics and 
the sense of smelling), A. Tschirch^) discusses the hitherto-known investigations and 
theories on the physiology and chemistry of the sence of smelling published by 
Zwaardemaker, H. Henning, Rupe and Ma}ewski,' Marchand, Ruzicka, and others. Basing 
on these investigations and his own experience, the author endeavours to answer the 
question : — Which are the conditions which must be complied with in order that a 
body shows an odour? Tschirch arrives at the following results: — 

1 . The phase of the aromatic must show a certain temperature, and it is likewise 
of importance whether the aromatic is dissolved, and which is the solvent. 

2. The substance must be readily soluble in air. 

3. The distribution-coefficient for the aromatic and ai^ must be favourable for air, 
hence in case of a mixture of equal quantities of aromatics the odour of such 
bodies will predominate which are most soluble in air. 

4. The distribution-coefficient for aromatic + air -<— > lipoid plasma of the olfactory 
cells must be favourable for the latter. 

5. If it is assumed that chemical reactions are set up between the aromatic and 
the plasma, the former must contain atoms, atom groups, or ions which are 
able to react with the plasma molecules. 

6. The osmophoric groups which generally are characterized by a strong tendency 
to react,, are osmophoric only conditionally, at any rate only in cases when 
they are able to react with the colloidal plasm of the olfactory cfells. The. 
general chemical structure, more specially the building-up of the aromatic is 
of minor importance. A system of the shades of odour basing on the con- 
stitution of the various aromatics can not be established. 

7. Tl^ sensation of odour is not caused by the aromatics, but by the very labile 
compounds formed in the colloidal olfactory cell-plasm (offering enormous 
surfaces) and mostly decomposing again instantaneously. These are eithe** 
adsorption compounds — which is less probable •— , or reaction-products betweei 
the aromatic (highly-ionised on account of its extreme dilution) and the olfactor 
cell-plasm which offers the aromatic a most extraordinary great surface in forn 
of olfactory hairs, dimples, or conicles. 



1) Joum. de Pharm. et Chim. VII. 23 (1921), 161. — «) SchweizeriscJie Apotheker-Ztg. 59 (1921), Mos. 17 
to 20. From a reprint kindly forwarded to us. 



Notes on scientific research. 123 

8. These are the compounds exercising the sensation of odour on the olfactory 
nerve which is then conducted to the brain. 

9, Hence, quite a series of conditions must be complied with in case that an odour 
is to be rendered perceptible. If one of them is not answered to and there is 
a missing link in the chain, no odour is noticeable. 

tCf. Odour is a chemical action on the sense of smelling. 

Tschirch speaks of the "solubility of the substance in air". In order to explain 
this, scientifically incorrect, expression we add that the author refers to a paper 
published by H. Erdmann^) who inferred, from the easy solubility of aromatics in 
liquid air, a specific solubility of there bodies also in gaseom air. For the sensation 
of smell, not the volatility of the substance is deciding, but a different property whiqh 
Tschirch terms solubijity in air. The author wishes to point out hereby that the 
molecule of the aromatic, which emits a different odour when in concentrated and in 
diluted state, undergoes changes due to the air. With increasing dilution a cleavage 
down to the ions is expected to pass off, as in the case of aqueous solutions. 

F. B. Hofmann^) has published a paper on the sense of smell basing principally 
on self-observation. Owing to a severe catarrh of the nasal cavity the author had 
nearly entirely lost his power of smelling, and but quite by degrees ^nd very slowly 
normal smelling sensation was recovered. During this period (several years), Hofmann 
undertook systematically a large series of experiments, the result of which is as 
follows: — 

In the beginning Hofmann was only able to perceive the odour of natural and of 
artifical musk in their characteristic peculiarity and apparently also in their full strength. 
Pyridine smelled strong, but not so unbearable as usually. Of other bodies, the author 
had a sensation of odour with acetone and, quite indefinite as to character, of t^obutyl 
and isoamyl alcohols. When in the following weeks the sense for smelling pyridine 
improved noticeably (the author made use of Zwaardemaker's olfactometer as modified 
by Zimmermann), also ofher substances which hitherto were odourless for him became 
noticeable. Ammonia and trimethylamine smelled strong; diethyl ketone, acetone, 
amylene hydrate, ether, and chloroform somewhat less strong; butyl and amyl alcohols, 
amyl acetate, butyrate, and valerate very weak, and thymol, toluene, and xylene 
extremely weak. Only a trace of odour was noticed, inter alia, with benzaldehyde, 
carvacrol, menthol, and phenol; yet Hofmann was able to differentiate between the 
odour of these bodies. No odour whatsoever was perceptible with asa fcetida, iodoform, 
mercaptane, scatole, and vanillin. 

Some months later Hofmann notice^ that many of the substances mentioned 
showed a strong smell, but quite different from their usual character. Normal behaviour 
was exhibited, in addition to musk, only by vanillin. Indole remained quite odourless. 
The author was particularly struck by the qualitative change in the different s^nielling 
sensations after their reappearing. Violets and ionone, for instance, smelled in the 
•--ginning like cigar tobacco, later on the true violet odour became perceptible. 

Even several years afterwards the author failed to perceive some special odour 
aracters. For him, putrefying albumen and scatole showed a faint sweetish odour, 
phuretted hydrogen, carbon disulphide, garlic, and various spices, such as caraway, 
abnormal, indefinite smell. 



*) Joum. f. prakt. Chetnie n. F. 61 (1900), 226. — ') Zur Theorie des (^ntchainnea, I. Pdrosmie-Studien. 
tschr. f. Biologie 73 (1921), Nos. 1 to 4. As per a reprint kindly forwarded to us. 



V* 



124 Report of SchimmelSCo. 1922. 

Hofmann concludes from his observations that most of the odoriferous substances 
act not only on a single, but on various peripheric receptive organs of different 
specific energy. Whenever a series of such receptive organs are acted upon and 
act together, combination smells are generated and the individual smells disappear 
more or less. The author considers this phenomenon to be the reason why some 
aromatics, when concentrated, show' an odour different from that in diluted stMe^). 
By taking for granted that an odoriferous substances acts on several receptive organs 
it might be readily explained why the odours of many chemically pure substances 
resemble each other, and why from newly-synthesised bodies specific new odours 
result which otherwise are not to be found in Natut:e. 

In a paper entitled, liber einen historischen Beitrag zur Theorie d^ Geruchsempfindung 
(On a historical contribution towards the theory of odour perception), H. Heller') cites 
and discusses a passage from a book published, in 1814, by C.W.G. Kastner, professor 
of physics and chemistry in Halle, and entitled, Einleitung in die neuere Chemie (Intro- 
duction into modem chemistry). The author proves that already more than one hundred 
years ago Kastner held views on perception of odour which highly resemble modern 
theories. Nowadays, we agree with Kastner that the senses of taste and of smell are 
in close relation to each other, and also that in both cases it is necessary for the 
actual sensation that the respective active body be virtually present. Likewise, Kastner*s 
opinion is correct insofar that we are only able to smell gases. We are unable to 
perceive liquid aromatics by their smell in case they are introduced into the nose. 
In Kastner^s opinion, sensation of odour is due to a disturbance of equilibrium. This, 
too, is correct. On the mucous membrane of the nose, the content of water in the 
membrane and in the surrounding air, under normal conditions, are in equilibrium; 
however, as soon as the inhaled air carries patticles of an aromatic, the conditions 
of osmotic and the chemical equilibrium are upset which makes the basis of sensual 
perception^). Finally, Kastner maintains that the sensation caused on the nasal mucous 
membrane is more unequivocal and less subject to errors than the sensation of sight. 
Heller agrees with this view (hitherto not contradicted) and supports it by proofs, the 
discussion of which^ however, would carry us beyond the scope of our Report, 

The same author^) demonstrates by various instances that chemical compounds 
which are generally said to show an offensive or unpleasant odour, when in a quite 
pure state, cause an entirely different and often even pleasant sensation of smelU 
sometimes, too, none at all. Fare acetylene, pure carbon disulphide, whose impurities 
show a putrid smell, show a pleasant ethereal odour. Likewise, various alkyl sulphides 
(t^oamyl, ethyl sulphides), even ethyl mercaptane may be freed nearly entirely from 
their unpleasant smell by heating with copper powder (decomposition being but feeble); 
the latter adsorbs the evil smell. Hydrogen arsenide, whose garlic-like smell could 
be hitherto regarded as characteristic for that body, is according to Thoms and Hess'^) 
odourless when quite pure, and when applied to the tongue causes a feeble sweet 
taste. (Of course these experiments were carried out with infinitesimal quantities.) 

Heller points out that these facts have not received due consideration in some 
recent investigations, e. g., in those of Kauffmann and of Henning on odour sensations. 
Hence, Kauffmann 's^) theory of the change of odour (with alkylamines, mercaptanes, 



») Cfr. the view held by Tschirch, preceding abstract. — «) Deutsche ParfUm.-Ztg. 7 (1921), 83. — 
») Cf. for this the above-cited paper by Tschirch. — *) Detitsche ParfUm.-Zig. 7 (1921), 123. — •) Ber. d. 
deutsch. pharm. Gea. 90 (1920), 488. — *) Ztachr. f. Psychologiey 2. AM. 1908, 217. 



Notes on scientific research. 125 

thio-ethers, Sc) and likewise Henning's^) theory of conipound odours which is based 
on the formul^r and the odour of (impure) carbon disulphide, are both untenable. 

The connection between constitution and odour are dealt with in a paper by 
Ml Guerbet*). ' 

In research work on olfactology it is of importance to examine at any given 
moment the condition of the observer*s sense-organ. According to H. Zwaardemaker^) 
this is done best (1) by establishing the accessibility of the nose to the air in respir- 
ation; (2) by testing the sensitiveness of the sense-organ. Whether the nasal cavities 
are normal or not can be ascertained, as the author proved years ago*), by breathing » 
quietly and briefly on a metal plate held below the nose: From the shape of the two 
breathing-spots each subdivided by a hiatus conclusions may be drawn as to the 
transmissibility of the air through the nose. The acuiti^ of the smell-organ is measured 
by means of the olfactometer, which conti-ivance we described as early as in 1904"). 

By means of an improved type of olfactometer the author found the following , 
limit values for a normal olfactory organ, expressed in tube-lengths for a just 
appreciable smell-sensation of the aqueous solutions:— concentrated solution of amyl 
acetate, 0.17 cm.; cone. sdl. of nitrobenzene, 0.19 cm.; 0.08 per cent. sol. of terpineol, 
023 cm.; cone. sol. of artificial musk (trinitrpwobutyltoluene), 0.18 cm.; 0.11 per cent, 
sol. of (commercial) allyl alcohol, 0.26 cm.; 0.26 per cent. sol. of guaiacol, 0,20 cm.; 
0.32 per cent sol. /Of caproic acid, 0.15 cm.; 0.38 per cent. sol. of pyridine, 0,11 cm.; 
cone. sol. of skatole, 0.28 cm. For obtaining a general notion of the sensitiveness 
of the observer's nose, the nipkel supply-cylinder may be replaced by a piece of new 
indiarubber tubing 10 cm. long with an interior diameter of 8 mm. An olfactory organ 
may be considered to be normal when its "minimum perceptibile*)" for new, unused, 
vulcanised caoutchouc lies at about 1 cm. of the olfactometrical scale. 

A camera inodorata, in which olfactometric experiments may be carried out 
regardless of any by-odours, has been devised by H. Zwaardemaker^). The camera 
is a box with glass walls 6f a capacity of 400 litres, the roof and the bottom being 
of aluminium. All wooden parts are equally covered with this metal which absorbs 
odorous matter but slightly. The box is placed on high legs, and the experimenter 
can pass his head from below through an opening that can be closed by a slide. The 
space may be rendered inodorous in a short time by means of an uviol or preferably 
a quartz lamp. But few odours are not destroyed by ultraviolet light. As the author 
demonstrated, in 1913, in conjunction with Tempelaar'), many odorous bodies are 
extremely sensitive to light, i. a., many esters, acetone, chloroform, bomeol, eucalyptole, 
eugenol, citral, terpineol, vanillin, coumarin, butyl alcohol, pyridirte, skatole. Some 
odour of ozone which may, be present after the illumination disappears soon. 

An olfactometer is attached under the slide at the bottom of the box, by which 
olfactometrical determinations can be made. By means of special contrivances, the 
inner tube of the olfactometer can be readily freed from any adhering scent. The 
observer must have closely-cropped hair and a qyite scentless skin. If necessary, 
the skin must be thickly powdered with talc, or covered with odourless vaseline. After 



») Henning, Der Geruoh. Leipzig 1916. — «) Joum, de Pharm. et Chim. VII. 22 (1920), 344. As per 
Chem, Zmtralbl. 1921, II. 414. — «) Perfum. Record 12 (1921), 308. — *) JHe Physiologie des Geruchs, Leipzig 
1896, •p. 72. — ») Cf. Report October 1904, 104. — «) Perfiim. Record 12 (1921), 243. — ') Cf. RepoH 
October 1918, 126. 



i ' 






126 Report of Schimmel S Co. 1922. 

this the .observer remains in the box for five minutes (while the lamp radiates) with 
closed eyes' screened by euphos-glass spectacles. 

The experiments showed that in the camera inodorata the minimum perceptibile Was 
on the average 25 per cent, lower than in ordinary surroundings. 

The camera may be used also as a camera odorata by volatilizing a measured 
quantity of odorous substance and carrying out the olfactometrfc measurements in the 
scehted atmosphere. 

The firm of Lautier Fils, of Grasse, have constructed an appliance called **evapol- 
factometer" and designed for the recognition and valuation of odours. The apparatus 
was invented by Oddo^), and it consists of a thermometer, the mercury bulb of which 
is surrounded by an electrical resistance, and a very fine polished silver sheath. 
A rheostat above the thermometer permits of varying the current intensity, and hence 
the temperature. In use, the compound perfume liquid to be tested is poured on the 
silver rod and the temperature increased slowly. The^ separate odours are said to 
evaporate according to their degrees of volatility and may be perceived singly and 
one after another. This new process of analysing odorous bodies claims to offer 
various advantages over the usual method of testing by a spill of paper. 

The sense of smell and the recognition of smells is rarely exercised and hence but 
feebly developed with most people. The following experiment was carried out at the Phila- 
delphia College of Pharmacy and showed to which extent mistakes in recognizing smells 
occur even with skilled persons*). A series of 15 liquid odorous substances was sub- 
.mitted to twenty men, all with a more or less complete pharmaceutical training. The 
purpose of the test ^as to identify the odour of each specimen. Oil of turpentine was 
the substance which was best recognized, by all except three, which called it in turn, 
oil of anise, oil of caraway, and pine oil. Alcohol was difficultly recognized by the 
majority, on the other hand, vinegar^) was easily identified. Oil of cinnamon was reported 
by three persons as oil of anise, oil of bitter almond, and oil of wintergreen. Kerosene 
and gasoline were confusing to quite a number. Two men reported gasoline as chloro- 
form, two others took kerosene for carbon disulphide. Creosote was judged by five 
as oil of clove, by five others as cresol.' Only two men failed to identify methyl sali- 
cylate, who took it for oil of peppermint. Benzaldehyde was judged twice as nitro- 
benzene, oil of orange eight times as oil of lemon. One man took ether for ethyl nitrite. 
Linseed oil was recognized by nine persons, ten reporting it as fish oil or cod liver oil,, 
and one taking it as neatsfoot oil. Th^ identification of oil of nutmeg was not attempted 
by three of the men, three reported oil of turpentine, one reported it as oil of colander^ 
and one as oil of cardamom. One of the students had no smelling sence for hydrogen 
sulphide and admitted that he detected only the most powerful odours. 

On former occasions, we reported on the interesting investigations by K. von Frisch*> 
on the sense of smell in bees. The same author^) publishes now numerous new experi- 
ments on the "sign-language*' of the bees. It could not be established beyond doubt 
whether the bees communicate by means of sounds; at any rate, however, the authoi 
was able to prove that the bees inform each other on the presence of food by some 
sort of sign-language. This communication is effected, in accord with the darkness ir 

1) Perfum. Eecord 12 (1921), 135. — ») R. R. Foran, Amer.Joum. Pharm. 93 (1921), 683. — ») Accordini 
to Weiss, vinegar acts not on the olfactory organ, but on the sensp of touch. Cf. Report October 191^ 70 
— *) BepoHs 1917, 121; 1919, 108. — ') Munch, med. Wochenschr. 1920, p. 566; 1921, p. 509. As per a separate 
copy kindly forwarded to us. 



Motes on scientific research. 127 

hive, not by the sence of sight, but by touch. As soon as a bee (the collector) 
has discovered a food-place, it pertonns a "searching dance" when returned to the hive, 
which causes the oHiers bees to swarm out in all directions and to search for the 
food-place. In cases where the crop emanates a blossomy smell the latter is noticed 
with the searching bee, and this smell is then traced. When the crop is abundant 
the collecting bee assists the others in searching by exhibiting its, own smeli-emanating 
organ (located between the 5. and 6. back segment of the body), and thus impregnating 
the surrounding of the food-place with its' own smell. 

About 40 essential oils have been investigated by Heinz'), of the Pharmacological 
Laboratory at Eriangen, with regard to their pharmacological ac^n. Although the oils 
are frequently mixture of quite different components, they often show the same action, 
insofar as the latter is based upon identical physical properties of the oils, e, g., volatility 
and solubility of lipoids. For instance, the odoriferous bodies have in common both 
the properties of local irritation, lasting, however, only a short time, and that of chemo- 
taxis, i. e., the attractive action on leucocytes. Owing to the solubility of the essential oils 
in lipoids, fats and oils, they easily permeate the skin protected by a layer of fat and hence 
assailable only with difficulty. Equally, the aromatics spread rapidly in the blood, since 
they combine readily wilh the blood corpuscles rich in cholesterol and circulate with them. 

Of details, Heinz deals with the action of peppermint oil on the liver'), of juniper 
oil on the kidneys, of thymol on the dental nerves, and of turpentine oil on the leuco- 
cytes. We content ourselves with this reference, as we have frequently reported on the 
pharmacological properties of these and of other essentia! oils'). Yet we wish to add 
that Heinz recommends an emulsion of milk with 5 per cent, turpentine oil for hypo- 
dermic injection, and that he introduces a powder for dressing wounds composed of 
sugar with 5 per cent, turpentine oil, which he terms "terpestrol". 

). C. C. Gunn and 0. H. Ttaut*) furnish some details on the carminative action of 
various essential oils, which, however, seem to contradict each other. According to 
Gunn, essential oils such as anise, peppermint, fennel oils, ^c, when diluted 1 : 20000, 
stop the peristaltic motion entirely. The same action is effected by local application 
of 0.5 cc. of a solution of 0.05 per cent, of the oils in Ringer's solution. The therapeutic 
action consists in: relaxation of the cardia, alleviation of excessive peristaltic move- 
ments, besides local irritation, such as hyperemia and sensation of heat. 

On the other hand, Plaut noticed, with an isolated bend of a dog's bowel {in gUu), 
marked increase of the, peristaltic motion. Previous treatment with atropine effected 
lessing of the motion, application to the bowel of cocaine neutralized the action com- 
pletely, and morphine was without any influence on the action of the essential oils. 
no explanation is given for this discrepancy which may be caused by the method 
adopted, or by the different action of different doses. 

A short paper by F. Marre") deals with the use of aromatics as sedative remedia. 

Aromatics of animal origin, such as mush, civet, casforeum, and ambra are known ever 

<ce on account of their sedative action. Fumes of ambra were employed as a remedy 

epilepsy, and later on inhalations of ambra were proved to possess an anti- 

asmodic effect 

') Hunch, med, Wochemchr. 68 (1921), 628. As per Deutai-Mi Parf. ZCg. J (1921), 157. — ■) Cf. BrritJit 
Toi. ed,) ISfll, 38. — ') Ct. out BegorUi under the heading Pkarmamlvgkal anit pkynotogkat Hotea. — 
/o«™. pftorm. niid eTjur. Therap. 18 (1920), 39 and 311. As per ratrap. Halhmonatuh. 36 (1921), 184, — 
■^Tfitm. modeme U {1921), 80. 



128 



Report of Sckimmel ft Co. 1922. 



Of odours ol vegetable origin showing a sedative action, the' , 
the lily, lily of the valley, carnation, orange, opopanax, vanilla, and h 
blossoms, such as the lily, tuberose, and honeysuckle, are known to ex 
action; by experimenting on animals the essential oils were prove 
the living organism, a similar action as <Alorofonn or ether'). 

Sores of various Hnde have been treated in sixty-eight cases 
terpeneless oil of lavender'). If the greater part of the Infected sores 
tory symptoms after several applications of the pure oil, it is then i 
to weaker solutions <1 tp 10 per cent). Gangrene was arrested immedi 
instances cicatrisation was complete in less than a month. In th< 
ulcers in particular, a weak solution has proved an excellent anti; 
results were obtained particularly with burns and scalds by the . 
terpeneless oil for four or five days, followed by wet dressings durin) 
and finally dressing with starch powder or bismuth. In the case ol 
the pure oil was applied, and then a powder of thymol iodide anC 
other cases, after removing the pus, the pure oil was injected and 
with a pad damped with the oil; this was renewed daily, and fina 
applied after cleansing the sore. 

G. and K. Cofi') report on the treatment of febrile tuberculosis 
intramuscular injections of menthol + eucalyptut oU. The authors inj 
times a week 0.5 to IjOcc. of the following mixture: — 0.1 g, iodin 
10.0 g. menthol, 10.0 g. eucalyptus oil, 20.0 g. castor oil, and give 
treatment of 168 poor or indigent patients as follows: — ^n> Patientt 
of the second and third stage, as well as infantine tuberculosis, ( 
be freed from fever by means of Berliner's mixture*), so that they m 
a treatment with "alt-tuberculin" without contracting fever, (b) T 
fever passes off lytically and without unpleasant consequences of 
during a tuberculin-treatment continual fever occurs, injections ace 
enable further application of tuberculin by depressing the fever. 
the lowering of the fever, the subjective complaints, such as pain 
perspiration, Qc, were in all cases alleviated or even removed, f'e, 
rature after injections of tuberculin have no bad influence upon tf 
culin in the second stage of pulmonary tuberculosis, whereas in the 
in temperature is generally associated with loss in weight,, hemop 
fever-depressing action of the Berliner mixture passes off by action 
seat of the disease as being the cause ot the fever. This was prov 
which demonstrated that during the treatment with the Berliner mix 
sensitiveness towards tuberculine showed a decrease. 

As has been shown by Macht") the anti^Msmodk action of thi 
alkaloids is due to the presence of the benzyl nucleus in the alka 
verine group. Simpler compounds containing the benzyl nucleus 
alcohol, some of its esters, and benzaldehyde, but not benzoic ad 
action. The antispasmodic properties are exhibited, as is demonstrat 



') Detailed studies on the Htter-eH 
also by Henning. Cf. Rrport 1S1«, 103. 
mowtah. a& (1921), 236. -~ >) Cori's recipe diCFers som 
— •) JiHi™. of Pdnnnoeoi, ond erp. ThtrBfi. » (1917), 2t 



Notes on scientific research. 129 

and P. Q. Row'), in a higher degree by veratryl and piperonyl alcohols, piperonal, 
vanillin, veratryi aldehyde, and (j- and p-hydroxybenzaldehyde. 

Since nothing is known as to the therapeutic action of the benzyl esters of the 
higher fatty acids and the aliphatic and aromatic amino-acids, and other sulpho and 
amino-aclds, the authors prepared a number of these esters, and determined the 
physical and therapeutical properties. The esters of the higher fatty acids were tasteless, 
colourless liquids — those of the unsaturated acids showed an unpleasant taste — or 
low-melting solids, which had neither an anesthetic effect nor an irritating action on 
the mucous membrane. Owing to the insolubility in water of tbese esters the usual 
physiological tests on animals were not entirely satisfactory. Clinical tests were there- 
fore resorted to, which demonstrated the antispasmodic action of these esters In 
asthma, dysmenorrhcea, high blood pressure, pytorospasm, and spastic constipation. 

The benzyl esters of p- and m-amidobenzoic acid showed an irritating effect on 
the mucous membrane and possessed local anesthetic properties. 

Benzyl lactate was also prepared but because of its irritating effect it was not tested 
clinically. 

the benzyl este»s of mixtures of fatty acids derived from natural fats had the equal 
therapeutic properties as the benzyl esters of the individual fatty acids. They are 
more readily hydrolysed by lipase than are the benzyl esters of aromatic acids. 

As Cnielsen and |. A. Higgins^) have cibserved, the peristaltic movanenU (observed 
in «(« with. dogs) are lessened by intravenous infection of a 5 percent, emulsion of 
benzyl benzoate or cinnamate. The latter ester is at least quite as effective as the 
beazoate, but is not quite so effective in lowering the blood-pressure. Benzyl cinna- 
mate shows a moderately toxic action; a small dog stood about 15 gms. after oral 
application without any harm. 

Frolilich and Grossmann') continued their experiments on the medicinal action of 
camphor*). A frog's heart, when under camphor treatment, reacted no more, on appli- 
cation of alternating current, by raging ("vmhlen"). The authors conclude herefrom 
that camphor is capable of improving the metabolism of the heart ventricle. 

G. loachimoglu °) was able, by application of camphor to a leech preparation, to effect 
increase of the tonus, and contractions of hours' duration. D-, 1-, and il.f-camphor 
showed the same action. Since thymol, of anthelminthic fame, causes a similar effect, 
the author believes camphor to be efficacious as vermifuge when applied as enema. 

Terpichin (a solution o( 15 per cent, turpentine oil with each 0.5 per cent of quinine 
and anesthesine in olive oil) is used for dermatologirat pHrpims and with various in- 
flammations. W. f^ro") prefers the intravenous injection of this remedy in lieu of the 
usual intragluteal application, since it proved to be superior to the latter. 

Trabut') recommends in the Irealmenl of diabetes a decoction of eucalyptus leaves 
(10 to 15 gr. to a litre of water and boiled down to one-half of its volume). The 
leaves of Evcalyptus divergicdor and E. roafrata act as well as those of E. GliAxdus. 

As to the medicinal use of terpentine oU, see p. 77 of this Report. 

On injections with solutions of bemyl bentoate, vide p. 92 of this Eeport. 

') .Toun. Amer. dum. Soc. 43 (192t), 361. — •) Joum. of Moral, nnd din. .naJ. « (1921), 388. Al per 
m. ZmtraOil. ISBl, III. 1173. — 1 CI. B.™Ji( (Gem. ed.) 1981, 63. — ') Arch. f. cxp. Pharm.^u. Path. 
(1921). 1. As perrAeroj., Haidmmiatoft.K (1921), 37e. — ')Arch.f., 
.- Therap.Hidimimatth. a&{i92l),S!6. — •) JCfin. IfocAenscAr. 1 (1922), 9 



Report op Schimmel a Co. 1922. 



Chemical Note$. 



In a paper entitled, "Some constituents of essential oils and their structur 
relations", |. W, D. HacWi^) endeavours to give an outline of the structural relation 
the above-mentioned constituents, and to illustrate by practical application the advantagi 
of structure symbols, the new chemical notation of oi^anic compounds, the presei 
method of notation occupying a vastjy greater space and annoying the printer Jn 
high degree. The old formula are replaced by geometrical devices which elimlna 
the customary symbols C, H, 0, M and represent their atoms by points from whi( 
one, two, three, or four lines, respectively radiate. A straight line — stards for hydrogc 
(H— H, assuming one atom of hydrogen at either and of the stretch), an angle ; 
represents water (h)^^)' *-^^ ^^6'^ ~'^ stands for ammonia (H~'**^i-i)i ^nd a cross -\ 

H 
for methane I H — C — H I . Where two stretches meet, one atom of oxygen is tocat£' 



(H-C-H I 



+1 for camphor, $c. 



where three or four meet, an atom of nitrogen, or carbon, respectively. Each organ 
compound belongs to a different type and a different class, such as hydrocarbot 
(o — , or R — H, the circle standing for the radical), alcohols (0-7, or R— OH), aldehydi 
(o-/', or R— CHO), ftc. The type of the compound indicates its chemical character ar 
reactivity, the class its general structural characteristics, either saturated or unsaturate' 
aliphatic or aromatic. Expressed by the new notation, ++ stands for ethane CHs— CH 

)<Z>' for ethylene CH!=CH,, Y | for hexamethylene CaH„, I ^ for benzer 

C»H«, i J for menthane, and |+ 

These examples seem sufficient to give the reader an idea of Hackh's notatioi 
Those who are interested in the study of the new system may resort to the origin, 
paper, where the notation pf 157 compounds occurring in essential oils is given ar 
their structural rclaiion is detailed. 

The salts of the higher fatty acids, when in solution, crystallise In the shape 1 
a spongy mass which, according to C. A. Cofman-Nicoresti '), shows a great power fi 
absorbing volatile oils. As little as 5 per cent, of the salts was sufficient for obtainir 
such "solid solutions". 

Hydrocarbons. 
A process for obtaining arontatu: hydrocarbons has been devised by A. S. Ramage'):- 
Hydrocarbons containing one or more alkyl groups are treated, In the presence of a cataly: 
such as fenous oxide, with hydrogen. The alkyl groups are hereby replaced by hydroge 

A process for the preparation of polyeydk hydrocarbom of the terpens series, U 
which a patent is applied by the firm of Schering, of Berlin*) consists in heating t) 

>) Joum.Amet:plmrm.Am.9i}920), W8. As per a wparale copy hindljr forwarded to us. — ^ Ohtm: 
and llruggiat 9S (19Z1), 854. - ') Am. Pat. 1365S« oE Ian. IS"", 1991. As ptr Chtm. Ztntralbl. IKBl, II. 5£ 
- ') Genu. Pat. Appl. C/W5I8, published [an. 12", IMS. 



Notes on scientific research. 131 

hydrazones of terpene ketones with mercuric oxide, or t|ie double salts of mercuric 
chloride and the hydrazones, after addition of the equivalent amount of alkali, in an 
indifferent solvent. By the interaction of the mercuric oxide and the hydrazones, 
difficultly-soluble basic mercury compounds are formed whose constitution possibly 
resembles that of the mercuri-ammonium compounds and which decompose, on heating 
in indifferent liquidSi according to the following equation: — 

CioHierN WH-HgOH — ► CoHie + N, + Hg + H^O. 

The patent specification contains details for the preparation of tricyclene from 
camphor hydrazone (crude yield, 78.3 per cent.), of d-cycZofenchene from d-fenchone 
hydrazone, and of aj?ocyclene from camphenilone hydrazone. 

The principal products resulting from the pyrogenetic decomposition of benzene 
are, according to E. PeytraP), hydrogen and diphenyl; 2C6H6 — >- CeHaCeHs + Hg. 
One-third of the hydrogen formed results either from a radical decomposition of part 
of the benzene into methane, carbon (graphite), and hydrogen, or (as is more probable) 
from a part of the diphenyl formed and then decomposed further. 

Benzaldehyde, when submitted to the treatment indicated, decomposed principally 
into benzene and carbon monoxide, besides into diphenyl, carbon monoxide, and 
hydrogen. In addition, a small amount of anthracene is formed due to condensation 
in the hydrogen atmosphere. As secondary products of the decomposition of diphenyl, 
carbon and methane were traced. 

A process for obtaining p-cymene from the waste terpenes (b. p. about 175°) 
resulting from the camphor synthesis, or the fractions boiling at 175° and at 160° of 
Swedish of Polish "turpentine" (pine> oils has been published by the Rheinische 
Campherfabrik'), of Dusseldorf. The respective fractions are chlorinated slowly at 
temperatures ranging from 10 to 80°, the reaction-product distilled with steam, the 
volatile oil heated with some zinc chloride and subjected to distillation. Yield about 
60 per cent of the primary material; it may be raised to 75 per cent, by heating the 
crude material with an inorganic or organic acid, or an acid salt, and by usiiig the 
fraction boiling at 175° for the chlorination. 

Ralph H. McKee and Leland J. Lewis') recommend fahsplitting reagents obtained 
from cymene, i. e., cymene stearosulphonic acid. The compound is obtained analogous 
to Twitcheirs*) method for preparing aromatic stearosulphonic acids. 280 gr. of oleic 
acid and 140 gr. of cymene were stirred, and 300 gr. oi sulphuric acid (66 deg. Be.) 
was gradually added, keeping the temperature below 35°. Further details on the 
preparation and purification of the product may be gathered from the original paper. 

On comparison with Twitchell's reagent, benzene and naphthalene stearosulphonic 
acids, and the "Kontakt" reagent, the cymene derivative offers, in the opinion of the 
authors, the following advantages: — It is more easily and cheaply made and can be 
produced as a uniform product. The fatty acids as well as the glycerin obtained by 
its use are both of a lighter colour. 

Terpinene. — Contrary to the other nitrosites of unsaturated bodies, whose structure 
is mostly bimolecular, the nitrosite of terpinene possesses the simple molecularity of 
C10H16O8N2, and it does not show the colour reactions characteristic of the dissociation 



^) BuU. 80C. chim. IV, 29 (1921), 44. — «) Germ. Pat. 819 162 and 319 163, July 14*^ 1921. Engl. Pat. 156329, 
Febr. 3^, 1921. — ») Americ. Perfumer 16 (1921), 175. — *) Joum. Americ. chem. Soc. 22 (1900), 22. 

9* 



132 



Report of Schimmgl S Co. 1922. 



(N,0,) 



i 



of the bisnitroso group. Since, however, the nitrosite, on treatment with caustic 
potash, gives rise to a body C20H81N8O4 (m. p. 163 to 164 o), and since it interacts 
with amines, with formation of nitrolamines — C(:NOH)— C(-NHR)== and splitting-off 
of MOaH, Wallach^) at a time was of opinion that terpinene nitrosite is bimolecular, 
at least in the solid state, and that the grouping NO2 was attached to the carbon 
atom by the usual nitrite-linking C— QNO, as in the genuine nitrosites. This view is 
not shared by H. Wieland and . F. Reindel *). The behaviour of dicyc?opentadiene and 

— c c — of ethylene shows that on addition of nitrogen trioxide NgOs to un- 

Aos saturated bodies ^^ew^Zonitrosites (fcisnitroso-nitro compounds) are formed, 
^Oj of the structure as given by the annexed formula. Equally terpinene = 
-t — J^'^-dihydrocymene containing a grouping of two conjugated double- 
bonds, is no exception to this rule. By catalytic hydrogenation of terpinene nitrosite 
(m. p. 153 to 154^), Wieland and Reindel obtained, besides a monovalent base, a 
diamine which was found to be 1,2-diaminohexahydrocymene and which was identified 
by its dibenzoyl compound (I, m. p. 165^) and the hydrochloride of the monobenzoylated 
diamine (m. p. about 290°, turning brown). Hence, terpinene nitrosite undergoes a 
partial reduction to 1,2-diaminohexahydrocymene, and both the NO- as well as the 
NOa-group are linked to the carbon atom by their nitrogen. By this reaction the 
structured formula (II) is established beyond doubt, where the authors have replaced 

the : C : NOH-group by the group * \^/ in order to indicate the insolubility in alkali. 

The interaction with alcoholic potash studied by Wallach^) and yielding the nitrite 
must be considered to be an intramolecular alkylation, and formula (III) must be 
attributed to the reaction product. The body CioHieOeNs obtained by Amenomija*) 
by action of nitric acid on terpinene nitrosite is, in the opinion of the authors, 
1 , 2, 2-trinitrotetrahydrocymene. 

CHs 



CHs 



CHj 



CHs 
C-NHCOCeHfi 



C-NO9 



CH— NHCOCeHft CH, 



CH 



CH, 



CHs 



NH CH, 



CH 



CH 



CHg 



M- 



CH(CH8)2 

(1) Dibenzoyl-1,2-diaminohexa- 
hydrocymene. 



CH(CH8)a 

(II) Terpinene nitrosite. 



CH8 

c— riOa 
/\c- 

C CHs 

CH(CH8). 



CHb 

I 



NH 



c 



CH 



(HI) CH(CH8)2 

Reaction product from terpinene nitrosite. 



On moslene, see p. 51 of this Report. 



Verbenene. — In a prior publication, Blumann and ZeitscheP) had proved that 
verbenol (I) splits off water readily on treatment with acid reagents and yields a doubly- 
unsaturated bicyclic terpene C10H14, verbenene. The authors prove now') that verbenene, 
which is isomeric with j?-cymene and which can be transformed into that terpene, 
possesses the structure of a dehydro-«-pinene (II). By oxidation by means of alkaline 
permanganate solution, verbenene was degradated to m-norpinic acid (III) by which 
the intactness of the tetracyclic system was proved. The conjugated position of the 



») Liehig's Annalen 356 (1907), 223. Sec also Eeport April 1907, 142. — «) Liebig's Annalm 424 (1921), 
92. — ») loc. cit. — *) Berl. Berichte 38 (1905), 2020. — ">) Cf. Report October 1918, 105. — •) Berliner 
Benchte 54 (1921), 887. 



Notes on scientific research. 



133 



double bonds was proved by the formation of the terpene from verbenol (1), by the 
value found for the molecular refraction (44.57, calc. for /^ 43.05), and by the behaviour 
of verbenene towards bromine. The easily-obtainable dibromide was strongly optically 
active,' the rotation being opposite to that of the primary material, and gave rise, on 
treatment with dilute potash solution, to an unsaturated glycol CioHieO? (IV; m. p. 141°) 
and to an apparently oxide-like body which was not examined further. The authors 
were unsuccessful in trying to replace the bromine atoms by hydrogen. On the other 
hand, dihydroverbenene (V; b. p. 158 to 159° [726 mm.]) was formed on treating the 
terpene with sodium and alcohol. (Cf. Semmler, On the reduction of a.phellandrene, 
Berl. Berichte 36 [1903], 1035 and 1753.) Dihydroverbenene, which may be taken for 
a ^-pinene, strongly resembled a-pinene in its physical and chemical properties, such 
as the formation of pinene hydrochloride on introducing dry hydrogen chloride, or of 
a nitroso body identical with nitrosopinene from the nitrosochloride. Hence the authors 
believe that a-pinene is primarily formed by the action of acid reagents. 

CH C COOHCH 



OHHC 



HC 



c 

^^(CH8)3 

cfcHs 

(1) Verbenol. 

COH 



CHs 



CH 





CCHb 

(II) Verbenene. 



(CH8)«C 



HOOC 

(ill) Norpinic acid. 




CH 
C(OH)CHs 

(IV) Glycol from verbenene 
dibromide. 




HX 



CH, 



CH 
CHCHs 

(V) Dihyidroverbenene, 
^-pinene. 




CCH3 

(VI) a-Pinene. 



Unene. — By repeated fractional distillation, in vacuo, of 15 litres of French turpentine 
oil, Pariselle^) obtained: — a-ijinene, b. p. 153.5 to 154.5° (760 mm.), or 62° (32 mnj.), 
doo 0.8748; [«]di50-43,48o nDi8ol.4690, rOt. disp. 1 (A = 589), 1.185 (A = 546), 1.44(A = 492)r; 
2 (I = 436), coefficient of viscosity 0.0141, mol. refr. 43.85, and i^-pinene, b. p. 163 to 164° 
(760 mm.), or 71 .5° (34 mm.), doo 0.8848, di5o 0.8728, [a]Di50 — 19.80° rot. disp. 1 (^ = 589), 
1 .1 (X = 546), 1.15 (^ = 492), 1.08 (?) (^ = 436). 

With hydrogen bromide, a-pinene yielded the solid pinene hydrobromide, m. p. 94°, 
b. p. 94° (12 mm.), [«]di50 +27.95° (in toluene solution)], and a liquid hydrobromide 
which contained the solid isomeride in the dissolved state. /^-Pinene showed exactly 
the same behaviour and gave a solid monohydrobromide with nearly the identical 
''^nysical constants, except [a]Di50 being —31.50°. By the action of bromine on a-pinene 
''riselle obtained the solid monohydrobromide, a liquid monohydrobromide, a dibromide 
.p. 150° with slight decomposition at 130°), andWallach's dibromide (m. p. 166 to 168°)*). 

By synthesising pinocamphone and o-pinene from monocyclic bodies, L. Ruzicka 
lid H. Trebler^) were able to prove the correctness of Wagner's pinene formula (I), 



1) Compt. rend. 172 (1921), 14«6. — «) Cf. Liebig's Annalen 264 (1891), 7. — «) Helv. chim. acta 4t (1921), 666. 



134 Report of Schimmel a Co. 1922. 

which hitherto was not quite fully established. By condensing the ethyl ester of pinonic 
acid with chloroacetic ester according to the method devised by Darzens') the authors 
obtained the corresponding glycidic dicarboxyllc ester and thence by saponification the 
' acid itself {II; m. p. 128° with evolution of carbon dioxide). When this acid waS heated 
to 230° it splitted off carbon dioxide and passed over into ho'mopinocamphoraldehydic 
acid Oil; b.p. 130 to 140° [3 mm.]; semicarbazone, m.p, 193 to 194°) which on oxidation 
with permanganate yielded homopino camphoric acid (IV; diethyl ester, b. p. 130° [1 mm.]). 
This acid was best transformed into pinocamphone (V) by the method of W. Dieckmann *), 

CH, CH, CH, 



'f. 



Or CHCOOH 

COOH 


HC|< 


^■ 


CH 
-^CHO 

COOH 


-C(CH.), 


1 




"-qcH.), 


\Jou 


H,CL 


^ 


1 JcH. 


CH 






CH 


dicarboiylic acid 
nonic acid. 


■IdBhydic acid. 





--"^COOH 


Hc<; 


COOH 




^C(CHrt 


HtC-.^ 


X--'"- 




CH 


(IV) Homo 


inocamphoric acid. 




(V) Pinocamphone. 

by condensation of the diethyl ester of the (IV), in xylene solution, with sodium. The 
hetonic acid ester formed primarily was saponified, with formation ot pinocamphone, 
by boiling with a 15 per cent, hydrochloric acid. The semicarbazone and the oxime 
of the (i, I-pinocamphone thus obtained were identical {as was proved by the melting- 
^oint of the pure substance and of the mixture) with (he corresponding preparations 
of Wallach') resulting from a d, i-pinocamphone from nitrosopinene by treatment with 
zinc and acetic acid. Since pinocamphone may be transformed into pinylamine and 
o-pinene by means of the reactions described already by the authors*), an uninterrupted 
way is given for the partial synthesis of o-pinene from a-pinonic acid. 

Hitherto it has been generally taken for granted that on addition of dry hydrogen 
chloride to pinene always pinene hydrochloride — bornyl chloride 0) is formed, 
O. Aschan") proved this assumption to be incorrect, as the isomeric liquid, tertiary 
pinene hydrochloride is formed in this reaction. This compound, stable only at a 
temperature below — 10°, partly splits off hydrogen chloride on treatment with aniline 
and yields pinene rotating in the same sense as the starting material. When the tertiary 
pinene hydrochloride is removed from tlie freezing mixture, it rises in temperature up 

') Crmpl. ,-aia. 189 (1904), 1214. — •) lAOig'i A 
~ ») Ct. BttriOtt (Getm. ed.) 19B1, 106. — ') Felenst 
Chem. ZtMraOd. 1921, III. 629. 



Notes on scientific research. 



135 



to 60 to 80° and rearranges itself to solid bornyl chloride. It is probable that whenever 
bornyl chloride is formed from pinene and hydrogen chloride/the unstable compound (III) is 
always formed intermediarily. . ' 

CH2 ■ CH2 GHg . CHs 

Z 



12 I 



HC 



-c(cti;,)a— ^CCHs HC' 



CHCl 



C(CH,)2 



\c/ 



CI 



CHa 

(1) Bornyl chloride 



crij CH 

(11) Tertiary pinene hydrochloride. 



Nopinene, when submitted 
to the same treatment, equally 
gave rise to the identical "V\^ 
tertiary pinene hydrochloride 
which with aniline passed 
over into pinene and not into 
nopinene. Since with the tertiary chloride the velocity of its rearrangement; at 0° 
exceeds its formation velocity from pinene and hydrogen chloride, it was not possible, 
even at a low temperature, to obtain it free from' bornyl chloride. Its odour is strangely 
suffocating, and it attacks the mucous membranes. The mixture . of hydrocarbons 
obtained on scission with aniline consists mainly of pinene, but contains also some 
dipentene, or limonene, and a still unknown cyclic terpene (in the fraction b. p. 162 to 167°). 

The action of hypochlorous acid on pinene, e;xamined years ago by Wagner*) and 
his collaborators, has been investigated afresh by G. G. Henderson arid J. K. Marsh ^). 
These authors found that the products obtained formerly, two chlorohydrins, pinol oxide, 
sobrerythritol, and nopinol glycol, are hot the primery products of the reaction, but 
are formed from Jhese by the action of the potassium hydroxide employed. Treatment 
of pinene (b. p. 156 to 157°) with a very dilute aqueous solution of hypochlorous acid 
yielded two crude products of which the one was soluble in water. This product was 
a mixture of three crystalline dichlorohydrins, C10H18O2CI2, which melted at 139 t6 140°, 
124 to 126 °^ and 155° respectively, together with a viscous, oily substance. The first of 
these dichlorohydrins (nitrobenzoate, m.p. 175°) gave reactions identical with those of the 
compound (m. p. 136°) prepared by Wagner and Slawinski. By direct synthesis of sobrerol 
dichloride (cis-l,2-dichloromenthiine-6,3-diol, m. p. 138°) from i-sobrerol the authors 
confirmed Wagner^s view that pinene dichlorohydrin (m. p. 139°) and sobrerol dichloride 
(m. p. 136°) are identical. (The mixture of both bodies showed the same m. p. 138°). 

Qn treatment with two molecules of aqueous caustic potash, the dichlorohydrin (I),, 
m.p. 139°, formed pinol oxide and i-pinol glycol-2^hlorohydrin (III) CioHi70jCl (m. p. 104 
to 105°) which after heating with -caustic potash solution gave rise to pinol oxide. An 

CHs 



I 
CCl 



OHHC 



HaC 



CHCl 



OHHC 



CHCl 



CH 
OHC(CH8)2 




CH, 



C(OH) 



HC 



\ 



CHCl 



H2C 



\ 



C(CH8)2 



CHt 



(II) Isomeric intermediary (?) pro- 
(1) Pinene dichlorohydrin (m. p. 139°). duct, chlorohydrin (m. p. 70 to 71 o). 



CH 

(III) PinolglycoU2-chlorohydrin 
(m. p. 104°). 



isomeric, but entirely different chlorohydrin C10H17O2CI (m. p. 70 to 71°; nitrobenzoate, 
m. p. 125°) was formed on shaking one mol. of the dichlorohydrin (m. p. 139°) with 
one mol. potassium oxide in a very weak aqueous solution. This body was readily 
transformed, by the action of water, into i-pinolglycoI-2-chlorohydrin, m. p. 104°. It may 






' • * .•<•.!" - 

'- \ I.' i""* 

:■ ''' • *•! 

. .; >• »,»v 









• •• i4-<i 



■m 



%:..^ 
: :-^i 



:\i^ 



s 






-va 



») Cf. BepoHa October 1896, 88; October 18»9, 63. — «) Joum. chem. Soc. 119 (1921), 1492. 



/. 



136 Report of Schimmel S Co. 1922. 

be assumed that the compound of the m. p. 70 to 71° results as an intermediary product 
in the preparation of pinolglycol-2-chlorohydrin from pinene dichlorohydrin (m. p. 139^). 

The dichlorohydrin of the m. p. 124 to 126° was optically active ([a]Hg~28,20) 
and was apparently 2)8-dichloromenthane-l,6*diol. With dilute aqueous potassium 
hydroxide it yielded optically active pinolglycol-2-chlorohydrin (m. p. 131^, some 
t-pinolglycol-2-chlorohydrin (m. p. 104^), and a trace of pinol oxide. The third di- 
chlorohydrin, m. p. 155^, was present only in a very small quantity and was likewise 
optically active ([«]Hg— 59.5^); it is perhaps a derivative of /^-pinene, a little of which 
may possibly have been present in the pinene used. 

The viscous, oily body (see above), when treated with a 10 per cent, potassium 
hydroxide solution, yielded pinolglycol (m. p. 124°), which was evidently formed from 
pinol oxide and furthermore from a dichlorohydrin. ^ 

Fractional distillation in vacuo of the oily primary product which remained undissolved 
in water yielded, besides some unchanged, pinene, some tricyclene dichloride, CioHieCU, 
m. p. 169 to 172°, identified by conversion into camphane, m. p. 154 to 155°. 

In a third paper on pinene*), L Ruzicka and R. Trebler*) were able to disprove 
the formula (1) for nitrosopinene, as suggested by Wallach'). It had been Wallach*s 
intention to explain, by aid of his formula for nitrosopinene, various cases of iso- 
merism which occur in connection with various derivatives of nitrosopinene. The 
nitrosopinene obtained from the nitrosochloride is different from, the nitrosopinene 
prepared from the former via pinylamine, pinocarveol, pinocarvone. Likewise, the 
amine formed on reduction of the oxime is not identical with pinylamine. In order 
to explain these differences in the oximes and amines, Wallach had suggested that 
when nitrous acid acts on pinylamine a migration of the endocyclic double linking 
into the semicyclic position takes place. Ruzicka and Trebler proved now that on 
ozonisation nitrosopinene yields an ozonide wh\ch on splitting up is transformed into 
formaldehyde (or fotmic acid) and i^onitrosonopinone (II, semicarbazone, m. p. 220°). 
From the ozonide of acetylpinylamine there results, by the same treatment, the acetyl 
derivative of a-aminonopinone, m. p. 120 to 121°. It follows from these reactions that 
in nitrosopinene (III) and pinylamine the double bond is in semicyclic position and 
that both bodies are derivatives of /^-pinene. This new formula for nitrosopinene is 
in accord with Bredt's rule according to which camphor derivatives, on stereochemical 
grounds, are non-capable of existance, whenever a double bond proceeds from a carbon 
atom which is in common with two rings. 

Since pinene nitrosochloride is optically inactive, the two oximes, in the opinion 
of the authors, must be geometrical isomerides. 

CHg CHg 

C CO C 

CrC"" -iCiMOH CH, ,C:MOH CH C:NOH 

C(CH8)2 ! ; C(CH8)8 I C(CH«), I 

CH^l ; ^ . CH,L ' . ICH2 CHa CHa 

CH CH CH 

(1) Nitrosopinene (11) J«onitrosonopinone. (Ill) Nitrosopinene. 

(Old, incorrect formula). 

As to the preparation of pinene nitrosochloride, see p. 137 of this Report . 



1) Cf. BeHcht (Germ, ed.) 1921, 106. — •) Hdoet. chim. acta, 4 (1921), 566. -- «) Liebufs Annalen 388 (1912), IK 



Notes on scientific research. 137 

Camphene. — The body m. p. 157^ known generally in literature as camphene hydro- 
chloride resulting from the treatment of camphene with an excess of gaseous hydrogen 
chloride should be termed appropriately isobornyl chloride^ as we learn from a patent 
application by the firm of Sobering^), since it is a stereoisomeride of pinene hydro- 
chloride, or bomyl chloride. The true camphene hydrochloride (hitherto unknown), i. e., 
the primary addition product of hydrogen chloride to 

camphene, is e^asily obtained by the action of hydrogen ^^^ ^^ C(CH8)« 

chloride on a solution of camphene, when care is taken | qy\ i 

to avoid. any excess of the acid. | | ( XHg 

Camphene hydrochloride occurs in snow-white crys- HgC CH ^^\ 

tals (m. p. 125 to 127^) and shows a strong odour of ^ u ...... .. 

' , V,.„ . .. «! «. *u i. * • u ^ Camphene hydrochlond.-. 

menthol diffenng enterely from that of pinene hydro- 
chloride or isobornyl chloride. The compound splits off HCl soon after its preparation, 
and readily passes oyer into isobornyl chloride, so it is stable only for a short time. 
Camphene hydrochloride, on shaking with water, or preferably on treatment with 
alkalies, is transformed nearly quantitatively into camphene hydrate. 

J. Schindelmeis^r*) reports on attempts to split off hydrogen chloride from pinene 
monohydrochloride by means of Reychler's reaction (with potassium phenate) with the 
object of obtaining camphene and camphor. Anhydrous potassium phenate (2 mol.) 
prepared with an excess of potassium hydfoxide was mixed thoroughly with pinene 
hydrochloride (1 mol.) and the mixture distilled immediately. After removing the 
phenols the author was able to prove, in the distillate, the presence of camphene 
(in shape of isobornyl acetate after heating with glacial acetic acid in a sealed tube; 
isoborneol, m. p. 212^; from the latter, camphene, m. p. 50*^, «Di^ ^nd of bornylene, 
besides some terpinene and diphenyl oxide (m. p. 28°, b. p. 246°). Since, however, 
this process allows but 25 per cent, of the pinene to be transformed into camphor, 
it is of no interest from a commercial standpoint. The oil^ of Abies sibirica, Ledeb. 
offers a more advantageous crude material, as it contains 35 to 50 per cent, of bornyl 
acetate. Schindelmeiser was able to split off the acetic acid readily and quantitatively 
by a very cheap process; the borneol obtained was successfully transformed into 
camphor on commercial scale by electrical processes. A Franco-)apanese company 
intends, as per Schindelmeiser, to obtain camphor on a large scale in Siberia from 
the oil of the Siberian pine. 

On a- and /^-pinene, from French turpentine oil, compare p. 74 of this Report, 

Limonene. — A process for obtaining limonene and pinene nitrosochlorides, worked 
out years ago by K. LoffP), is published by H. Rupe*). It gives far better yields than 
the usual method (with ethyl or amyl nitrite) and consists in introducing a mixture 
of nitrous gases and hydrogen chloride into a solution of the hydrocarbon. The gases 
must be mixed in the correct proportion and must react at a temperature as low as 
possible. If hydrogen chloride is in excess only a green oil results with but very 
little crystalline nitrosochloride, the amount of which otherwise reaches 90 per cent, 
of that calculated*^). 






1) Germ. pat. appl. C. 29517, Sept. 25, 1921. — *) Pharmacia 1921, N^ 1 (Reval). As per a copy kindly 
forwarded to us. — *) Uber Beduktionen in der Beihe der cydischen Oxime und Nitrosochloride. Dissertation, 
Basle 1916. — ♦) Helvet. chim. acta 4 (1921), 149. — *) According to Wallach (Terpene und Campher, 2""< ed., 
p. 69) the preparation of nitrosochlorides by Tilden's process (introducing vapours of nitroxyl chloride into the 
chloroform solution of the terpenes at — 10^) is troublesome. Wallach's method (treatment with amyl nitrite 
and concentrated hydrochloric acid), however, works quickly and satisfactorily. 



138 Report of Schimmel § Co. t922. 

The investigation of the se^qtiHerpenes by means o( the usual oxidation 
or with application of heat, has hitherto not been very satisfactory. L R 
J. Meyer') undertook to elucidate the constitution of these bodies by ; 
dehydrogenation method. For this reason, the author heated cadinene (b 
136° at 13 mm.) with sulphur to 200 to 265°. After repeated distillation w 
they arrived at a naphthalene hydrocarbon CibK,b (b. p. 157 to 158° at 12 n- 
2920 at 720 mm.; d'^0.9792; n^..^ 1.5851; mol. refr. C«H,6/r calc. *4.73, fc 
which was transformed into the picrate CjiHjiOjMi (m, p. 115°) and regene 
the latter, hence was obtained in the pure state. 

The hydrocarbon behaved lilie a fully saturated body when treated with a 
bromine in carbon disulphide, or of potassium permanganate. On mixing with a 
solution of trinitroresorcinol the hydrocarbon yielded the styphn'ate CnHiiOgTis, 
By reduction with sodium and ethyl alcohol the authors obtained the dihydro 
ChHji, (b. p. 151 to 153° at 12 mm.) which was oxidised already by dilut 
ganate solution with formation of acids and which gave no addition-pn 
picric acid. 

The authors obtained likewise from a traction b. p. 125 to 138° (12 mm.) 
cadinene from East Africa copaiba balsam oil by treatment with sulphiir produi 
the identical picrate of the m. p. 1 15°. Hence other sesquiterpenes occuri 
AfrJcan copaiba oil, provided they are derivatives of naphthalene, must contai 
nucleus as does cadinene. 

On tetrahydroatractyletie, vide p. 48 of this I&port. 

Concerning machihne. see p. 48 of this Reporl, 



A process invented-by C. Paa!') for the preparation of inactive atronell, 
geraniol) by reducing geraniol with hydrogen In presence of palladium or pi. 
been patented in Switzerland'). 

G. Vavon and |. Detrie*) publish various details on the preparation of cj 
by hydrogenating phenol. The yield of cj/dohexanol differs but slightly {• 
thirds of the phenol used) even if the details of the process are varied wi 
velocity of the reaction is great; 400 g. of phenol, dissolved in 300 g. of a 
added by aid of 15 g. platinum up to 100 litres of hydrogen per hour, hiyd 
proceeded far less smoothly when the hydroxy! group was absent, or w1 
linked to an alcoholic or acid radical. Ci/cbhexanone was proved to appea 
mediate product and disappears again, as the reaction passes on. 

TeTpimol. — By heating terpin hydrate with an organic sulphonic acid, 
with quinoline sulphonic acid, R. Marchand°) obtained terpineol. 

On condensing citronellal with acetic anhydride R. H. Pichard, H. Hunter, V 
and H. Smith de Pennington*) obtained only two (and probably no more) o 
possible isomerides of i^opvkg'A. these two being I- and i-o-isopulegol. M 

') CI. Germ. Pal. 298193, Aug. 7, 1918. — ■) Swisi 
rv. 1323. — ') Compl. Tfnd. IJB (1921), 1231. — 
ItHI, I1.3S9, See alto p. 141 of Ihii Report. — •) 





. HtlvU. 


ckim. 


<.a„i 


(1921), 


505. 


Dec. 17 


, 1»1». 


Aspt 


^rChm 


1. z™(. 


■»(W. ■ 


153605, 


Dec, 9, 




As pe 


r am. 


Zmt 


S«. IIJ 


(1920), 


1248. 









Notes on scientific research. 139 

of th^ isopulegyl acetates rarely amounted to 50 per cent., it was probable that the 
aldehyde taking part in the condensation is the pure dextrorotatory compound of the 
formula CH, : C(CH8)CH2CH8-CH(CHi,)CHaCHO^). 

The hydrogen phthalate of the mixture of alcohols obtained from the condensation 
product could be separated by the fractional crystallisation of the magnesium and 
strychnine salts. Magnesium 1-isopulegyl phthalate, C86H4208Mg '61120, m. p. 111^; 
strychnine salt, m. p. 205°; l-isopulegol, b, p. 88 ^ (10 mm.); d-a-isopulegol (still con- 
taining, apparently, about 10 per cent, of 1-wopulegol), d^^ 0.9172; [a]Di9.5o + 29.3<^. On 
oxidation with chromic acid at 50°, gave isopulegones which gave identical lasvorotatory 
oximes (m. p. 121°, volatile in ,steam) and semicarbazones (m. p. 171°. When reduced 
by hydrogen, the alcohols formed l- and a-neomenthol respectirely, both of which, when 
oxidised, gave Z-menthone. 

The authors then give extensive tables on the constants of 1-isopulegol and its 
esters with the f^tty acids (C2 to C14) and igraphs on the rotation of the esters as 
influenced by temperature and wave-length. 

Menthol. — In a paper entitled, "Contributions towards the knowledge of derivatives 
of ^-menthol** Y^-wr Kenntnis der AUeitungsprodukte von I- Menthol) ^ E. A. Luck^ reports 
on some preparations obtained by him from ^menthol and menthone. By heating of 
menthol with concentrated, sulphuric acid for one hour he claims to have obtained 
a sesquiterpene CisHs* or C8oH4« (sic) brownish-black, thickish mass) and furtheron, 
by nitration, a nifrosasesquiterpene (! nitrosesquiterpene) C80H47NO2 (decrepitating on 
heating). Luck prepared also a menthyl cyanide ^nd herefrom a menthane carboxylic 
acid (termed by him methylene mentholic acid [sic]; white needles, the m. p. of which 
could not be kept constant [sic])^ the corresponding aldehyde, and from the latter the 
secondary (!) alcohol, and a ketone. 

All these bodies are enumerated with their constitutional formulas (as Luck imagines 
them to be) but without the least proofs of identity, without giving the necessary 
constants, or any analytical results. It is desirable that the autor may supplement 
his work in this respect and thus elucidate its results. 

BorneoL — A process has been published '^) for the preparation of borneol from 
turpentine oil, consisting in treating, the oil with tetrachlorophthalic acid and decom- 
posing the resulting dibornyl ester of the acid with alcoholic caustic soda solution. 
A mixture of one pt. tetrachlorophthalic acid and 4 pts. turpentine oil, or ccude pinene 
is heated for twelve hours to 106 to 108° th^ for two hours to 125°, and finally for 
six hours to 140°. After cooling the unattacked terpenes are removed by steam or 
vacuum-distillation and the residue, mainly dibornyl tetrachlorophthalate, is saponified 
by alcoholic sodium hydroxide. The bomepl, purified in the usual manner, is optically 
active and free from isoborneol. The yield amounts to 17 to 18; per cent, of the crude 
pinene employed. A large portion of the pinene as well as the tetrachlorophthalic 
acid is recovered. • 

If an organic solvent, such as anisole, a ketone, or an aromatic ester, is added 
to the mixture of pinene and acid prior to the heating, the reaction passes off more 
smoothly and the yield is raised up t6 29 per cent.*). 



*vr 



*) Cf. the paper by Prins, Chem. WeeJebl. U (1917), 692; Beport 191S, 123. — «) Apotheker-Ztg. a& (\92\), 
279. — ^*) -JFtibriques des produits. chimiquea de-Tbann etde Mulhouae. Pr. Pat. 510002, Nav. 25, 1990.. Brit. 
Pat. 144604, Dec. 3, 1919. Germ. Pat. Appl. F. 47011 published fan. 12, 1922. — *) Brit. Pat. 158533, Nov. 1, 
1920. (Add. Pat. to Brit. Pat. 144604.) As per Joum. Soc. chem. Industry 40 (1921), A. 561. 



140 Report of Schimmel S Co. 1922. 

According to another process devised by L. Schmidt^) the bornyl and isobornyl 
esters of organic acids are obtained in a good yield and free from by-products when 
these acids are heated with pinene or pinene-containing oils with an addition of boron 
trioxide. This latter reagent acts as a general condensing agent for pinene and organic 
acids by which pinene is esterified in a short time quantitatively even in open vessels. 
It is said to offer particular advantage to act on the mixture with boric, metaboric, 
or tetraboric acids on the anhydrides of the organic acids: For instance^ 13.6 pts. of 
pinene or turpentine oil, 9 pts. of glacial acetic acid, and 1 pt. of boron trioxide are 
heated to its the boiling point under a reflux tube, until the ester content increases 
no more. The ester mixture is washed with water and fractionated in vacuo and yields 
on saponification with alcoholic potash pure borneol + woborneol with a m. p. of 197 
to 199^. The unchanged boron trioxide can be used again. 

The process may be modified^ by substituting the boron trioxide by so-called 
mixed anhydrides of boric and of organic acids, such as boric acetic anhydride. This 
mixed anhydride, a simple additional product of the formula: — 

is preferably prepared in the cburse of the reaction. For instance, 136 kg. of pinene, 
60 kg. of glacial acetic acid, 10.2 kg. of acetic anhydride, and 2.3 kg. of boron trioxide 
are heated together for several hours on a water-bath, the reaction-product is rinsed 
with water as soon as the ester- content has reached a maximum, and the acetates of 
borneol and t^oborneol are obtained by fractional distillation. Saponification yields 
a mixture of pure borneol and woborneol, m. p. 197 to 198°. 

F. Martin^) started some experiments on the acetylation of borneol and isoborneol. 
His investigation culminated in the result that in estimating borneol or alkylborneol 
the alcohol must be heated for three hours with 3 parts of acetic anhydride and some 
sodium acetate up to 145 to 150°. With less time, or less acetic anhydride, acetyl- 
ation remains incomplete, as Martin states. (The acetylation was performed in an 
oil bath at a temperature close to the boiling point.) 

Contrary to these statements it is quite sufficient when in the quantitative acetyl- 
ation of borneol, equally so of geraniol, menthol, and santalol, 10 ccm. each of the 
alcohol and of acetic anhydride are boiled for one hour with 2 g. of sodium acetate. 
Years ago*) we established, by way of experiment, the correctness and praicticability 
of this method. 

According to L. G. Wesson**), \sobornyl ester and camphene are obtained by heating 
a mixture of a carboxylic acid and of pinene hydrohalide with some zinc, the proportion • 
of which not exceeding 5 per cent, of the pinene hydrogen hallde employed. 

Carvomenthol. — When reducing a-phellandrene nitrite with sodium and alcohol, 
W^lach and Herbig*) had obtained, in addition to tetrahydrocarvone (carvomenthone) 
and tetrahydrocarvylamine, Hetrahydrocarveol (/^carvomenthol), but they abstained from 
examing the resulting alcohol for optical isomerism. V. Paolini'), on repeating these 
experiments, found that two isomeric forms of ^carvomenthol are generated in the 



■• 



Germ. Pat. Appl. Sch. 50927, Oct. 3, 1921. — «) Germ. Pat. Appl. Sch. 53704, Oct. 3, 1921. Add. to 
Appl. Sch. 50927. — ») Joum. de Pharm. et Ghim. VII. 23 (1921), 168. — *) Report April ^910, 155. -- 
») U. S. Pat. 1372382, March 22, 1921. As per Ghem. Zentralhl. 1921, II. 1063. — •) Liibig'a Annalen 287 (1895), 
378. — '') Bend, della B. Accad. dei Idncei 30 (1921), 265. As per a separate copy kindly forwarded to us. - 



Notes on scientific research, 141 

process. The tetrahydrocarveol obtained from nitro-«-phellandrene (a-phellandrene, 
b. p. 75° at 15 mm.; diso 0.848; an*- 81^30'; tipao 1 .4769) by reduction with sodium 
and absolute alcohol showed the following constants: — b. p. 218° (corn); dwo 0.9073; 
Wd —10.83°, nuiso 1.463. From this alcohol the author prepared, by the cold process, 
the hydrogen phthalate of ^parvomenthol (m. p. 89°; [a]D — 45°4') which yielded 
on saponification pure 7-a-carvomenthol (b. p. 218° [corr.]; dis© 0.9074; «£>— 20.38°; 
ttDiso 1.463). From the mother liquor of the carvomenthol phthalate mentioned above 
a second, syrupy hydrogen carvomenthol phthalate was produced, which on trans- 
formation into its silver salt (m. p. 175 to 176°) yielded furtheron ^/^-carvomenthol 
(b. p, 218° [corn]; dig© 0.9071; [«]d— 8.63°; noiso 1.463). Paolini proposes to term the 
isomeric carvomenthols obtained by him^) from carvone, for sake of differentiation, 
(^-/-carvomenthol ([«]d + 1-82°) and ^-/-carvomenthol ([«]d — 1 .83°). 

Furthermore, Paolini') succeeded in obtaining from d-carvone, by following ttie 
directions given by Vavon^), on reduction with hydrogen and platinum, a carvomenthol, 
the constants of which were in accord with those of Vavon's preparation, with exception 
of the rotation (Md— 2.75°, instead Md— 24.7°). Paolini proved the products with 
different rotatory power to consist of mixtures of optical isomerides. Either the one 
or the other isomeride preponderated, according to the more or less complete process 
of the reduction. From carvomenthol (Mb— 2.75°) the author, by aid of his so-called 
cold process*) {via the di-(Z; /^-carvomenthyl phthalate, m. p. 85°, Md +38.53°), Was 
able to separate two isomeric compounds:— d, /^-carvomenthol (b. p. 218° [corr.]; 
di50 0.9074; [a]H-8.29i°) and Z,/5-carvomenthol (b.p.218° [corr.]; diso 0.9073; Md" ^-54°; 
noiso 1.463; identical with the one of the two isomerides resulting from nitrophellandrene, 
see above). 

Terpin hydrate. — According to a patent granted to the Societe Landaise du terpin^ol% 
terpin hydrate may be obtained from turpentine oil by means *of the following contri- 
vance: — A wooden vat, lined with lead, and filled with turpentine oil and dilute 
acid, is connected with two pumps of acid-resisting metal. The suction pipe of 
the one pump dips into the acid, that of the other into the oil, whereas the discharge 
pipes terminate in the oil and the acid respectively. On putting both pumps in 
motion a very close mixture of both acid and oil results within a short time, yielding 
terpin hydrate. 

Terpin hydrate is, according to R. Marchand'*), obtained in almost theoretical 
quantity and in the crystalline state on mixing oil of turpentine (one pt.) with a 
23 per cent, sulphuric acid (2 pts.) and shaking vigorously in an atmosphere of nitrogen 
or carbon dioxide for about 90 hours. 

Concerning the estimation of terpin hydrate, see p. 113 of this Report 

p. Lipp and C. Padberg*), with the object of studying the behaviour of sipotricyclol (I), 

a derivative of the hitherto unobtainable cyclopropano\ (II), prepared the first-mentioned 

alcohol from tricyclenic aoid amide (III), which, owing to the lability of the trimethylene 

ig was primarily degradiited according to Hof mann-Jeffreys ') down to opotricyclyl- 

Jthylurethane (m. p. 114 to 116°). In this reaction, tricycloyl-apotricycyl-urea (decomp. 



1) Cf. Bericht (Germ, ed.) 1921, 113. — «) Rend, della R. Accademia dei Lincei 80 (1921), 371. As per 
print kindly forwarded to us. — ») Cf. RepoH October 1911, 150. — *) Fr. Pat. 522657, Aug. 14, 1920. 
:e also Chem. Zmtralhl. 1921, IV. 1328. — ») Brit. Pat. 153606, Nov. 10, 1920. As per Joum. Soc. chem. 
,dustry 40 (1921), A. 716. — «) Berl. Berichte 64 (1921), 1316. — ') Berl. Benchte 30 (1897), 898. 



142 



Report of Schimmel a Co. 1922^ 



p. 238 to 239° [corr.], on slow heating) resulted as by-product, the iwcyanat 
in the main reaction acting with some of the unattached amide: — 

CeHuM:C:0 -f H^N- CO ■ CH,, = CeH^- NH ■ CO ■ WH ■ CO ■ CjHii 
Careful saponification, performed by fusing with solid caustic pot^h, yiel 
tricyclylamlne CgH„ISH,, m. p. 104° (unsharp), besides campheniione and can 
With the object to characterise the unstable apotricylylamine, the authors 
the body in reaction with, inter alia, phosgene, obtaining thereby as priitiary 
product a liquid compound, probably ajiotricyclyl isocyanate. The latter was tra 
by aniline into opctricyctyl-phenyl-urea. partly also into symm. di-apotricyclj 
C,H^-NH C,H„ MH 

>C0 ■<— C,H„N!CO — > >C0 

CH, -NH CHuMH 

AjwtricyclylphcDylurea, 4p(i1ricyc]yl laocyanale. Di-ofwlricyclylurea. 

On diazotising the hydrochloride of ajwtricyclylamine with sodium niti 
fricydol resulted, the reaction passing off fairly well; intermediarily, a comi: 
stable nitrite was formed. The alcohol irpotricyclol (m, p. 75 to 80° [i 
b. p. 82 to 86° at 12.5 mm.; phenylurethane, m. p. 121.6 to 122° [corr.]), on 
to t^ie air, deliquesces in the course of a few hours forming a viscid oil. Whi 
with a. dilute mineral acid, equally when heated (without water, by hetisati 
current of dry hydrogen, ayotricyclol yields quantitatively campheniione. Wi 
phoms pentachloride, apotricyclol passes over into campheniione dichloi 
m. p. 168 to 169°.. Ethereal solutions of the alcohol, on treatment with, 
sodium, yielded, without evolution of hydrogen, the sodium compound of cam[ 
pinakone (V) from which the methyl ether was obtained, dimethyl sulphate 
quantitatively, and methyl iodide only partly. 
, H,e— CH CH, H.C- - CH 



CHiCCH. 



CH,, 



\ 



CH,C-C 



H,C- 
H.C 



(1) Ajiotricyclol. 




(11) cvclop 


CH - CH, 


H,C- 


— 


r 

CH,CCH. 




CHs 


1 


HC 


C- 



(IV) Camphenilons dicfiloridc. (V) Sodium compound of campheniione pinacone. 

As to optical investigations of geranid and citronellol, vide p. 116 of thi: 

The publications by Fromm and Klein on dibanol (see p. 36 of this Eeport 
Muller on the constitution of reumd (see p. II 6 of this ifepor/) are discussed by H, 

') IMUiJie Parf.-Ztg. 7 (1921), 22. 



• ] 



Notes on scientific research. 143 

On a new a^fi-ketonic alcohol, CgHtoOa, compare p. 150 of this Report. 

From atractylol, Seisi Takagi^) obtained, by reduction witii ^hydrogen and platinum 
in glacial acetic acid, dikydroatractylol C15H28O as a viscid oil, [a]Du'o+14.9°. 

, , , 

Aldehydes. 

K. W. Rosenmund and F. Zetsche*), by catalytic dehydrogenation by means of the 
"copper-quinoline-nitro-body" and of oxygen, obtained from primary aliphatic, aromatic 
and equally hydrocyclic alcohols the aldehydes, from secondary alcohols the ketones. 
Tertiary alcohols remain unaffected. The following examples are cited by the authors: — 
benzophenone from benzhydrol (yield, 92 per cent.), "fermentation*' valeric aldehyde from 
"fermentation" amyl alcohol (80 per cent), acetaldehyde from ethyl alcohol (52 per cent.), 
propionic aldehyde from propyl alcohol (5 per cent.), isobutyric aldehyde from i>obutyl 
alcofiol (75 per cent.), o-chlorobenzaldehyde from o-chlorobenzyl alcohol (86.2 per cent.), 
fural from furyl alcohol (74 per cent.). The method is particularly suited with the 
difficultly, or non-volatile, alcohols; with the volatile alcohols, the method offers no 
advantages compared with the usual processes. 

The method worked out by Rosenmund and Zetsche") for the catalytic preparation 
of aldehydes from the corresponding acid chlorides lends itself likewise to the prepa* 
ration of polyaldehydes, as the authors found in community with Chr. Flutsch*). The 
following aldehydes were obtained by this method, with an average yield of 75 to 
85 percent.: — octanedial = suberic dialdehyde (di-semicarbazone, m. p. 183 to 185°; 
dioxime m. p. 152°); phen»dimethylal-t,3 = isophthalic dialdehyde, m. p. 88 to 89°; 
phen-dimeth'ylaI-1,4 = ^erephthalic dialdehyde, m. p. 116°. Orf/iophthalic dialdehyde, 
however, was unobtainable from the o-phthaljc acid chloride, probably the o-acid 
dichlorides are rearranged to the asymmetric form owing to the palladium chloride 
formed in the reduction. 

The following process for preparing aromatic hydroxyaldehydes has been patented 
in the U.^ K. in favour of the Society chimique des usines.du Rh6ne*): — Phenols on 
their derivatives are treated at suitable temperatures with formaldehyde in presence 
of a nitroso cqmpound, such as nitrosobenzene, nitrosonaphthalene, or j?-nitroso- 
dimethylaniline. If necessary, a condensating agent, e. g.j hydrochloric ^cid, is added. 
When the reaction has passed off the solvent is removed by distillation and the hydroxy 
aldehyde worked up as usual. 

The specification deals with the preparation of vanillin by starting from guajacol, 
formaldehyde, and j9-nitrosodimethylaniline. In the same manner anisic, protocatechuic, 
jo-hydroxybenzoic, and salicylic aldehydes are obtainable. 

Closely related to this process is the method specified by H. Haakh®): — Phenols, 
or derivatives thereof, are allowed to react with formaldehyde, or bodies splitting off 
formaldehyde, and aromatic nitroso compounds, e. g,, jp-nitrosodimethyl(ethyl)aniline, 
7)-nitrosophenol, in presence of a condensing medium (hydrochloric acid). By this 
method, anisic aldehyde may be prepared from anisole, and vanillin from guajacol. 



1) Joum. pharm. Soc. Japan 1921, No473. Of. also p. 47 of this Report. — •) Berl. Berichte 54 (1921), 

2033. — ») Cf. Beport 1918, 122. — *) Berl. BericJite M (1921), 2888. — •) Brit. Pat. 161679, April l3, 

1921; cf. also French Pat. 523407, Aug. 18, 1921, and Swiss Pat. 95560, Nov. 1. 1921. — •) Brit. Pat. 157830, 
Febr. 17, 1921. As per Chem. Zentralhl. 1921, IV. 121. 



r '< 



144 



Report of Schfmmel £( Co. 1922. 



Polymerisation of the most unstable acrolein to insoluble disacryl may be preve 
as was found by Ch, A^oureu, Cti. Dufraisse, P.Robin, and ]. Pougnet'), by add 
small amount of phenols or bodies containing such, such as pyrogallol (in propc 
t:1000), pyrocatechol or hydroquinone (1:500), gallic acid (1:250), or ethereal t 
solution (1 : 100). Extracts of tanning agents act in the same manner. These ph 
are likewise capable of arresting the once started polymerisation of acrolein, 
aklehyde, when treated wifh these agents, remains stable for years, provided tl 
is kept in the dark and at a temperature not exceeding 30°. 

Citral. — E. Knoevenagel and G. Oelbermann') have continued the work q 
first-named author^) on testing the constitution of compounds of the citral serii 
optical methods. The values observed by the authors of the specific normal exall 
of citral were in good accord with the figures observed formerly by v. Auwers 
Eisenlohr, as well as with those found by the last-named investigator for the s] 
— C(R):CH-CHO (E.rR,„.l.25; E^m.p. 45 percent.). Whereas a preparation of Citral 
keeping for 48 hours at a temperature of — 190° had suffered a slight change 
refractive index rising from 1.48786 to 1.48821), another preparation remained unchi 
after the same treatment. Afterthree months' standing in the same sealed bottles 
preparation, on optical examination, showed a strong increase in density and a dec 
in the molecular retraction. Possibly, it was the case of polymerisation, or oxid, 
or of both. 

With jtKeuiJoLOn one, the authors obtained values equally in good accord with 
recorded by Eisenlohr for the system — C(R) :CHCH : CH-C(R): (Ei^R.r,. somf 
above 2.7; E-dhr. above 110 percent.). The optical constants remained unchi 
after cooling the preparation down to —190° for 300 hours. 

From i«eurfoionone, ^'-ionone acetate was prepared according to Rnoevenage 
means of acetic anhydride with addition of sublimed ferric chloride. B.p. 145 to 
(15 mm.). Basing on the values read off tor the exaltations (E-Reir, +0,29 and + 
E i^Disp. + 7 and + 8 per cent.) the authors suggest formula (1) for the acetate, alth 
they admit that various isomerides may be present. This assumption is rem 
probable by the wide b. p. range of the freshly-prepared acetate, the main pa 
which boiled from 113 to 150° at 11 mm. No alteration of the optical values 
noticed after cooling down to —190'= during 300 hours. 

For iso-Y^ionone, obtained from the preceding acetate by boiling with alec 
caustic potash (b, p. 128 to 129° at 13 mm.) the author suggest formula (11) in 
of. the exaltations found (E.iReir. +2.22 and +0.39; Ei^w.p. +10 and +14 pert 
Cooling down to — 190°, for 300 hours, did not affect the body; hpwever, afte 
hours' standing in an open vessel the molecular refraction, by oxidation, rose 
1.49805 to 1.50311, and after 17 hours to 1.50350. The semicarbazone, m.p. 189° 
identical with a semicarbazone obtained in the same manner from y-ionone ac 

By abstracting water from v-ionone with zinc chloride, the authors obtainei 
fractions of a hydrocarbon (not quite pure, b. p. 90 to 122° [12 mm.] and 135 to 
[21 mm.]), concerning the constitution of which nothing certain could be stated 
the optical data or the chemical reactions (preparation of an oxidation-product). 

The optical dispersion observed with «-citrylidene acetoacetic ester was s 
what too low, since that body is easily rearranged into the i?-isomeride and ther 



sing acrolein. Germ. Pat. AppI, M/64903, April 7, HBl. 
') Cf. Hlimrt ISin, t«. 



Notes on sciemtific research. 145 

is difficultly obtainable in the pure state. In view ot this circumstance and of the 
optical constants found by them the authors regard the formula (111) of the ester'), as 
suggested by Steinle, as the correct one. 

From a dtrylldene acetoacetic ester the authors prepared, via the a-isoester, a-Mo- 
ionone. In order to make the methods of preparation agree with the optical data, 
t^oevenagel and Oelbermann assign to tills ketone formula (IV) in lieu of formula (II) 
hitherto accepted which they suggest for tM-y^ionone. 

When examining /^-citrylidene acetoacetic ester, the optical constants were not found 
to agree with the formula propagated by Mechtersheimer') which constitutes a simple, 
"disturbed" conjugated system. The optical data would agree best with formula (V), with 
cumulated double bonds, the presence of which, however, has not been proved hitherto. 

CHj^^CHa H.Cv^CH, 

C C 

i 11 

c c 

H,C<^CH-CH = C- 0-CO-CH, H,Cr>CH-CH,— CO-CH, 

I ■ I I ! 

HtC\ yCH CH, H,CL JCH 



I) PttudiHoaetie acetate. 



HaCv 

" -- CH— CH,-CH,-C = CH-CH = C-CO— CH, 

C0-0C,f1, 



>C- ( 
H,C/ 



HC(<^ ^CH-CH, 


-CO-CH, 






H.el^CH 

c 

1 

CH, 




CH-CH,-CH, 


-C = C = CH-CH-CO-CH, 
1 1 
CH, CO-OCH, 


(IV) ,«./«.ioiione. 




■IV) ff-attyM 


ene aceloaceUc eiter. 



Prom the ^-ester, a hydrocarbon was prepared according to Mechtersheimer by 
means of zinc chloride, which was oxidised by a mixture of nitric and sulphuric acids. 
The resulting body, a solid of the m. p. 154°, has not been examined further. 

The formulx for j^-v-ionone, A-wocitrylidene acetoacetic ester, and fi-isoionone^ put 
.forward by Mechtersheimer agree approximately with the values observed by the authors. 

On benzaldehyde, see p. 90 of this Report. 

Concerning a specially devised flask for the estimation of phenylaeetaidehyde, 
cf. p. 114 of this Heporl. 

Salieylic tddekyde and acid are obtained, as per an American Patent 1380277, 
May 31, 1921 of |. M. Weiss and C. R. Downs'), by oxidising o-cresol in the. vapour 
phase with a gas containing oxygen in the presence of a metallic oxide as catalyst. 

■) Cf. nspori IMfl, 148. — ') Cf. Btfi-ni 1919, 1«. — >) Joirm. S.x. ehm. Inrf. M (Itel), A. 561. 



Report or Schimmel £i Co. 1922. 



As to the preparation ol hetones from secondary alcohols, see p. 
present Report. 

In order to supplement earlier Investigations'), P. Sabatier and B, Ki 
new details on the catalytic . reduction ol henzaldthyde and ol aronjafic fee. 
of copper. The metal required for their experiments was prepared by ; 
at 200°, of black tetracupric hydrate. At 350°, benzatdehyde was reduc 
toluene, and carbonic oxide. Contrary to the reduction performed- forn 
nickel, the carbonic oxide was not reduced to methane, but remained i 

Acetophenone and ethylphenylketone were-reduced catalytically by > 
to ethylbenzene (b. p. 135°) and propylbenzene (b. p. 158°), Under identi 
benzoyl propanone was transformed into acetophenone (fairly good amoui 
aldehyde, ethyl alcohol, and ethylbenzene. By reducing benzoquinone over ( 
nearly exclusively hydroquinone, m. p. 169°, resulted, besides some wat 

Carvone. — A. Muller") was successful in preparing crystalline benzal 
hitherto has been obtained by the usual condensation reactions merely as 
product'). The condensation of carvone with benzaldehyde passed of 
alcoholic potash lye at a temperature not exceeding + 2 to + 3°. The f 
to 180° (10 mm.) of the reaction-product constituted the raw material for I 
of two isomeric benzalcarvones, the residue forming the amorphous 1 
already byWallach'). After several weeks' standing, a crystalline body 
the viscous benzalcarvone fraction, ^^-benzalcarvone, . m. p. 114 to 115' 
(a — 8.15° of a 1 per cent, alcoholic solution in a 100 mm. tube). The res 
carvone, b.p. I9.I to*ig3 (10 mm.); duo 1.041; [n]o + 152.30°, contained still 
amount of the ^-isomeride. Neither of the isomerides (which showed i 
bricK-yellow halochromism respectively) yielded an oxime or a semicarbaz 
carvone yielded an addition-product with hydrogen chloride, a dark bron 
heating gave off a fair amount of hydrogen chloride. On reduction with sc 
merides yielded benzyldihydrocarveol, the phenylurethane of which (m. p. 2. 
identical with the derivative of benzyldihydrocarveol obtained from benzald 

By means of the method founded on the absorption of ultraviolet li 
proved that on the one hand the curves tor /''-benzal carvone and benza 
the other hand those for o-benzal carvone and benzaldjhydrocarvone wet 
identical. This behaviour shows that both ^-benzal carvone and benzali 
identical structure, the former being, therefore, ,d-3-benzal carvone. 

How the o-isomeride is constituted remains still an open question, 
di hydro carvone may exist also in a second form. As compared 
(["Jd + S^.S"), the values lor [o]d with a- and /?-benzal carvone (+152.5' 
are exceedingly high. Both isomerides demonstrate very satisfactorily that 
aromatic radicals into the nucleus, i. e., by accumulating the double linhin; 
is markedly increased. 

According to JW. JWatsui and S. Shimizu'), menthorte can be reduced 
in sulphuric or hydrochloric acid solution to menthol. The best result! 

't Ct. Sabatier, La attalyat m Mmie ^nyanique, 2"' ed,, p. 190 io 196, — ") Qnupt. ™ 
— ■) Bert. BfnoMc 54 (1921), 1471. — ') IieWs'<Annnfen 106 (1899), 274. — ')M>m.Coa. 
245. At pec ,7™,™, Soc ,a™. Jnd. 10 (1921). A. 162. 



' Motes on scientific research. U7 

when using an amalgamated tin or lead cathode^ the cathode solution constisting of 
a mixture of 75 percent, sulphuric acid (40 to 45 cc.) with 94 per cent, alcohol (35 to 
40 cc.) at a temperature below 15^. The current used is 6 to 8 amperes per 100 sq. cm. 
at 11 to 13 volts. The yield of menthol is only 25 p.er cent, and the product was 
difficult to purify. An oily by-product is always obtained, which is a more highly 
reduced body, possibly menthane. 

By reducing thujamenthone with hydrogen and nickel at 280^, M. Godchot*) obtained 
dimethyl-l,2-wopropyl-3-c3/cZopentane, a liquid of terpene-like odour with the constants:, 
b. p. 148.to 149<^, di6o 0,793, nouo 1.4364. The same body had been prepared years ago 
by Godchot and F. Taboury*) from dihydrocamphorone. On treating thujamenthone with 
magnesium methyl iodide, Godchot obtained a mixture of two isomeric trimethyl-1,2,3'-i$o- 
propyl-4-cydopentenes which on further reduction with hydrogen and nickel at 180^ yielded 
the same body, trimethyl-l,2,3-isopropyl-4-qydopentane (b. p. 157 to 158<^;. dwo 0.7833; 
noiso 1 .4326), likewise with a terpene-like odour. 

Additionally, the author prepared a new bicycHc ketone, dimethyl-2,3-isopropyl-4- 
cyc/opentylidene-dimethyl-2,3-wbpropyl-4-cycZopentanone-l, by condensing thujamenthone 
by means of calcium hydride^). This new product was a light yellow liquid with a cam- 
phoraceous odour and the constants: t.p. 182 to 184^ (12 mm.); duo 0.9123; noiso 1.4825. 

Camphor. — By acting, with sodium isoamylate on cs^phor at 140°, in presence of 
an excess of t^oamyl alcohol, F. Martin^) obtained in a good yield, a mixture of alkyl 
derivatives of camphor and borneol ("camphol"). He then treated the reaction product, 
dissolved in benzene, with potassium permanganate and obtained isoamylcamphor 
(b. p. 273<^; apwo 5922^^) [in alcoholic solution]; semicarbazone,'m. p. 188°). By reducing 
the reaction-product of camphor and sQdium tsoamylate with sodium and absolute alcohol 
the author arrived at a-white greasy body smelling of borneol; b. p. 190° (61 mm.); 
dJI 0.9611; 00^6.55°^) (in alcoholic solution), which consisted of a mixture of stereo- 
merle bodies. On heating, for three hours, at 140° with the equal part of acetic an- 
hydride and some sodium acetate, the body yielded acetyli^oamylcamphol (b.p. 169 to 
170° [30 mm.]; d^ 0.9402; «d + 7.42° [in alcoholic solution]; phenylurethane of iso- 
amylcamphol, m. p. 111°). 

H. Rupe and W. Diehl®) prepared the following derivatives of hydrcm/methylene 
camphor :— methylene camphor-phenylhydroxylamine (m. p. 106 to 107°), the methyl 
ether of this body (m. p. 75 to 76, very sensitive to light; on exposure to sunlight the 
compounds deliquesces to a brown mass and separates a sublimate of delicate yellow 
needles, m. p. 196 to 198°, probably camphor quinone, the ethyl ether of methylene 
caniphor-phenylhydroxylamine (m, p. 162 to 164°), the i?-nitroben2oate of the same body 
(m^p. 179.5 to 180°). On reducing methylene camphor-phenylhydroxylamine, anilido- 
methylene camphor resulted (m. p. 165 to 167°), which was identical with the anilide 
obtained by Bishop, Claisen, and Sinclair^) by condensing hydroxymethylene camphor 
with aniline. 

By heating camphor and fural with sodamide in benzene solution, Wolff^) arrived 
at fural camphor, m. p. 64°, easily soluble in ether, alcohol, and benzene, less soluble 



1) C(mpt. rend. 172 (1921), 686. — •) Btai. soc. chim. IV. 18 (1913), 601. — ») Cf. Compt. rend. 109 (1919), 
62. — *) Joum. de Pharm. eb Chim. VII. 21 (1921), 417. As per Bull. Rourc-Bertrand Fils, April 1921, 104. 
— •) The direction of rotation is not given. — •) Helvet. chim. acta 4 (1921), 388. — ') Liebig's Annalen 
281 (1894), 358. — «) Compt. rend. 172 (1921), 1357. 

10* 



148 



Report of Schimmel S Co. 1922. 



J . . ' 

in light petroleum. When trying to reduce it to furyl camphor by catalytic reduction 

according to Sabatier and Senderens in presence of nickel, it was completely reduced 

to tetrahydrofurylcamphor, b. p. 166^ (14 mm.). 

Following the process worked out by Haller and Bauer*) the author prepared, mCi 
the organomagnesium compounds:— phenylfuryl camphor CioHisO'CHCCeHs) -04^180, 
m. p. 1 14°, benzylfurylcamphor, doHisO • CHCCtHt) • C4H8O (viscid oil); i?-tolylfurylcamphor, 
CioHibOCH(C6H4-CHs)C4H80, b. p. 2340 (17 mm.); i>-anisylfuryl camphor, C10H15OCH 
(CaH4- OCH8)-C4H80, b. p. 2550 (17 mm.). 

In a later communication, the author publishes the molecular refractions and the 
specific rotations of the above-mentioned compounds, which agree with the constants 
found formerly t|y Mailer and Muller") with the condensation-products from camphor 
and aldehydes. Furalcamphor shows a strong exaltation of the molecular refraction, 
the specific rotation, and the molecular dispersion, which is caused by the double bond 
linked to the furane nucleus and which disappears on reduction. 

I 

In connection with earlier work done on mono- and dialkyl derivatives. of camphor^), 
A. Haller and P. Ramart^) communicate that the amide of dimethylcampholic acid shows 
the m. p. 81 to 82° and not, as stated before*^), 72 to 73°. On reducing this amide with 
sodium and absolute alcohol, the authors obtained, on rectification, the nitrile of dimethyl- 



/CH(.CHs)2 
campholic acid C8Hi4<^ 



(b.p. 131 to 1330 [14 mm.], 245 to 247° [ord. press.]). 



On heading with sulphuric acid to 85 to 100° the nitrile ag^jn passes over into the 
original amide (m. p. 81 to %2^). When the nitrile was reduced with sodium and absolute 
alcohol, dimethylcampholamine (b. p. 123 to 124° at 20 mm.; Mdko +30.1°) resulted in 
quantitative yield. By reducing the phenyl ester of dimethylcampholic acid (b.p. 190 to 
195° at 30 mm.) — not though with the ethyl ester-r-with sodium and absolute alcohol, the 
authors obtained dimethylcampholic alcohol (b. p. 139 to 140° at 20 mm.; Wde*© + 32°). 

As to the preparation of camphor from pinene hydrochloride see p. 137 of this Report. 

Epicamphor. — In continuation of the paper by J. Bredt and W. H. Perkin jun.*) 
which dealt with the preparation and the properties of epicamphor, Perkin jun. and 
A. F. Titley') have prepared some derivatives of Z-epicamphor which they compare with 
the analogous bodies obtained from the isomeric (Z-camphor®). 

When ^epicamphor is treated with sodium and isoamyl formate in presence of 
ether, hydroxymethylene-Z-epicamphor is formed (m. p. 89°, turning but slowly yellow 
and viscous; semicarbazone, m. p. 197°) to which the authors assign, in analogy to 
the constitution®) assumed for hydroxymethylene-<i-camphor, the formula (I) 



CHs 



CH 

C(CH8)2 



CO 



co- 



CH- 



O 



CH.2 



CiCHOH 



CHs 



CHs 

(I) Hydroxymethylcne-epicamphor. 



C(CH8)2 COH 

il 
C CH 

CHs 



(II) Lactone of hydroxyketodihydroepicampholenic acid 

(tautomeric formula). 



1) Compt. rend. 142 (1906), 971; 14« (1908), 717. — «) Ibidem 128 (1899), 1370. — ») Cf. RepoH 1919, 160. 

— *) Compt. rend. 178 (1921), 682. — ») SepoH 1919, 161. — «) Cf. RepoH April 1914, 140. — ') Journ. 
chem. Soc. 119 (1921), 1089. — ») LieUg*8 Ann. 281 (1894), 314; 866 (1907), 251. — SeW. Ber. 80 (1897), 243. 

— ») Journ. chem. Soc. 95 (1909), 171. 



Notes on sciENTiPfc research. 149 

The substance gave a viotet coloration when ferric chloride was added to its 
alcoholic solution, and exhibited mutarotation to a slight extent only, and that in 
an opposite sense to the mutarotation of the corresponding camphor derivative 
(["Id of a freshly prepared benzenic solution rose [rom —125.5° to —130.5° after 
24 hours). Benzoyloxymethylene-epicamphor melted at 106°; aminomethylene-i-epi- 
camphor, m. p. 122°, was obtained by heating hydro xym ethyl en e-epi camphor with 
' aqueous ammonia; it does not exhibit mutarotation, contrary to the corresponding 
camphor derivative. Anilinomethylene-i-epicamphor, m. p. 101 °, no mutarotation; 
^-n a phthyl am inom ethyl ene-i-epi camphor, m. p. 109 to 110°, slight mutarotation. 

By heating I- or if-epicamphoroxime with sulphuric acid of 20 per cent, the authors 
obtained /-epicampbolenonitrile (b. p. 145° [100 mm.], ["]d^27.4°, passing over by 
hydrolysis into /-t-epicampholenic acid, b. p, 166° (30 mm.), [<i]t, — 38.4° and d-ep'i- 
campholenonitrile <b. p. 146 to 147° [100 mm.], [a]B+26.2°; rf-epicampholenic acid, 
b.p. 164 to 165° {30 mm.], [«]o + 39.2°). 

- Attempts to prepare ;?-epicampholenomtrile and its derivatives under the identical 
conditions as for obtaining /S-campholenic derivatives'), were unsuccessful. 

On reduction, /-epicampholenonitril is converted into J-epicamphylamine, b. p. 128° 
<100 mm.). 

When Z-epicamphoienic acid is oxidised with potassium permanganate, the main 
product formed is a mixture of syrupy acids from which a hetonic acid (semicarbazone, 
m. p. 203°) could be isolated. In addition, there is 'formed the lactone of hydroxy- 
ketodihydroepicampholenic acid (li), m. p. 80°; [b]i, -|- 45.8°. On oxidising the syrupj 
acids from the permanganate oxidation with chromic add, an optically active, monobasic 
acid, (semicarbazone, m. p. 168°) was obtained. 

Piperitone, — In their paper on the ketone piperitone contained in various eucalyptus 
oils, H.G.Smith and A R. Penfold*) had arrived at the conclusion that piperitone is 
either J'-menthenone-3 or J'-menthenone-3. L. Givaudan 8( Co.*) qh, 

were able to prove that the properties of the ketone — except in I 

its rotatory power — answered to the .J'-menthenone-3 prepared yx 

originally by Wailach*) from a trihydroxyterpane m. p. 120°, sub- HjC/ \CH 
sequently found by us") in Japanese peppermint oil and by Roberts*) 
in the oi\ of Cymbopogon gennaarensis. Hence, Givaudan i!( Co. regard njL^^LO 
piperitone as identical with -J'-menthenone-3. We wish to add that, CH 

although this conclusion does not seem to be fully proved, yet J-l, 

piperitone appears to be a d'-menthenone. The reason for our opinion HjC/ ^CHi 
has been given in our preceding Berkht (Germ, ed.) p. 24, footnote. j'.Menihenone-3. 

W. D. Cohen') tested various alcohols as to their power of reducing bemopMnone 
when exposed to sun-light. In all cases, whenever a reaction took place, benzopinacone 
was produced. The presence of water retarded the reaction. The reducing action was : — 
with methyl alcohol, 100 per cent,, (?i/dohexanol, above 90 per cent., benzyl alcohol 
about 80 per cent., geraniol about 1 7 per cent., citronellol and cinnamyl alcohol per cent. 
of the ketone. The alcohols were transformed respectively into formaldehyde; cydo- 
hexanone; triphenylglycol, resin, a little benzaldehyde; citral. 

This reduction of aromatic ketones is a photochemical process and hence the 
reaction-velocity independent of the concentration of the benzophendne. The oxidation 

') Cf. KnH. Bet. 30 (1897), 243, 405. - >) Cf. 
(1921), 80. - ') r-JiWfl'sAiinnien 889 (190S1, 271. - 
— ') Hfc. trai. Mm. J-inrs-Bn* 8« (1921), 243. As pc 



3t«n. cd.) lesi, 24. - 


•) Pir/\w,. fl«:n 


dn 


October 1810, 97. - • 


Cf. mi,oH iM' 




«(,■«(«. nei, 111. 785. 







150 Report of Schimmel ft Co. 1^2. 

of the alcohols, however, being, a purely chemical reaction depends in its sp 

concentration of the alcohol. ' 

A new optically active 'i,f4-ketonlc alcohol CgHigOi composed of equal 
of acetaldehyde and benzaldehyde and possessing the constitution CefitCOC 
or CaHsCHOH-COCH, has been obtained by C. Meuberg and |. Hirsch') bj 
an enzymatic process. The authors proved with Uiis synthesis, where two 
unite by a fermentation process anij form a ketone, that an enzyme exists 
linking straight-lined carbon chains. This new enzyme connecting carbon w 
was termed "carboligase". However, a direct union of acetaldehyde and bei 
by fermentation could not be effected, but it succeeded when the biological pi 
carboxyacetaldehyde, i. e. pyruvic acid, or also sugar, was employed. Tl 
proceeded in the following manner: — A mixture of sugar, or pyruvic acid 
the juice of macerated yeast), and benzaldehyde was left to stand for thret 
was then filtered and, extracted with ether, after the fermentation had come 
The residue of the ether was a light yellow oil with a pungent odour re 
benzyl alcohol (b. p. 102 to 156° at 15 mm.) which gave a strong" reaction w 
nitroprusslde and which precipitated instantaneously cuprous oxide from col 
solution. 0.1 ccm- of the oil dissolved in 10 com. of absolute alcohol, showec 
of —0.75^ in a 100 mm. tube. On standing at the air, signs. of de compos 
as a smell of benzaldehyde, were noticed. The authors were unable to- obtaJi 
fracti'on boiling within narrower limits, in spite of repeated distillation, but 
successful,!" preparing various derivatives of the product: ~ phenylhydrazone 
semicarbazone, m. p. 189°; thiosemicarbazone, m. p. 204 to 205"; p-nitropher 
m, p. 26+ to 265° — which served for identifying the product and as a pn 
correctness of the formula) given above. 

It could not be elucidated in which manner the fermentation of sugar ( 
racemic acid passes off in presence of benzaldehyde. The authors leave 
discussion whether a specially reactive form of acetaldehyde is formed by tl 
of pyroracemic acid with carboxylase, which unites with benzaldehyde, or v 
biological condensation starts already with benzaldehyde and pyroracemic 

Phenols and Phenol Ethers. 

Garvacrol. — According to Gibbs and Phillips'), a good yield of carvacrol 
from y-cymene sulphonic acid only when the process is carried on in an 
With reference to this statement, A. W. Hixson and R. H. IVlc.Kee') claii 
obtained a good yield (76 per cent.) of carvacrol from ^cymene sulphonic 
working at ordinary pressure. The carvacrol of Gibbs and Phillips (prepar 
without pressure) is said to contain 6 to 8 per cent, of thymol, which wo 
detection by the method of analysis used by Gibbs and Phillips. 

D. C, L Sherk') has published a thesis entitled, Thymol and carvacrol p 
which we discussed some details in our last Bericht (Germ, ed.) 1921, ; 
addition to the compounds mentioned there the author prepared the alki 
nitroso carvacrol and nitrosothymol by dissolving the nitroso phenols in the 



im. Zlicht. lie (1921) 


282. As per a special copy kindly forwarded 


OaO, U7. >) Jm 


■T>. mfl. ,ns. Chiw. 13 {1920), 296. - •) Thesi 


. ISSO. from a copy 


kindly forwarded to m. 



Notes on scientific research. 151 

quantity of 2N-alkali made up free from carbonate, ^nd evaporating to dryness in a 
vacuum desiccator. The salts were coloured red or blue, corresponding either to the 
nitroso or to the isonitroso (oximido) type. The silver salt of nitrosocarvacrol was 
at first greenish-brown, turning later to olive and finally brown. 

For identifying both phenols, the benzoyl derivatives of the nitrdso compounds are 
particularly useful:— benzoyl nitrosothymol, (from alcohol, m. p. 109 to 110.5°; no oxime 
obtainable); benzoyl nitrosocarvacrol (from alcohol, m. p. 85 .to 87°; oxime, obtained by 
treatment with hydroxylamine hydrochloride and sodium bicarbonate; m. p. from benzene, 
156 to 157° with evolution of gas). Alkali transforms the oxime into nitrosothymol. 

By treating the alkali salts of both nitrosophenols with methyl iodide in alcoholic 
solution, the author obtained nitrosocarvacrol methyl ether (m»p.39°) and nitrosothymol 
methyl ether (liquid). 

. Isosafrole. — S.Tiagaii^) reports on the various geometrical isomerides of i^osafrole, 
on which Hoering and Baum^) had published a paper, some time ago. When saft*ole 
is rearranged to isosafrole, the stable trans-form is obtained best by heating 1 pt. safrole, 
0.5 pt. potassium hydroxide, and 1 pt, 98 per cent, alcohol up to 94 to 95° for four to 
five hours. The labile cw-form, which on heating passes over into the other isomeride, 
is formed when using less alkali and more alcohol and at a lower temperature. The 
author describes the following preparations: — cfcisAisosafroIe (b> p. 242 ,to 243°; 
d^ 1.1162 td 1.1168; iidiso 1.5630 to 1.5632; picrate, m. p.. 68.5°); t (transj-isosairole 



(b p.247to248°; d^l.l230to 1.1235; nniso 1 .5730 to 1.5736; picrate, m.p.73.5 to 74°). 
The dibromides of both isomerldes differ merely by the angle of rotation: — ct^dibromide, 
Wd»o + 13.35°, fra««-dibromide, [alojoo + 4.45°. 

By distilling in vacuo or by heating with potassium hydroxide, the f-dibromide 
yielded the c-monobromide (b. p. 168 [19 mm.]), and vice versa, the odibromide gave 
the f-monobromide (b. p. l54° [19 mm.]) of isosafrole. cw-lsosafrole monobromide as well 
as ^dibromide, when heated to 70°, readily split off hydrogen bromide with formation 
of piperonyLallylene CH202:C6H8C i CCHs (m. p. 41 to 42°, b.p. 249 to 251°). On 
the other hand, ^monobromide and odibromide yielded piperonyt allylene only when 
heated to 150° and with an excess of alkali. 

On heating the monobromides with zinc and alcohol, the author obtained the 
corresponding wosafroles. This reaction furnishes a method of obtaining, from c-iso- 
safrole, via the bromine compounds, ^rart^-derivatives, and again leads back to the 
initial body. 

By oxidising both isomerldes with' potassium permanganate or ozone, the same 
body, piperonal, resulted. 

A new method for the preparation of the alkamines of anethole, isosafrole, and 
methylwoeugenol has been published by J. Takeda and S. Kuroda*). The pseudo-ureas 
of these bodies, obtained from their dibromides with urea, are constituted, in the 
opinion of the authors, as demonstrated by the annexed formula, and on treatment 

with acetic anhydride and sodium acetate they yield the acetyl R-CH NH 

derivatives and the acetylated oxazolidones. These bodies are | "^C : NH 

broken up, on boiling with alkali, more readily than the y-ureas R'*CH 0/ 
and lend themselves, therefore, preferably for the preparation of the alkamines. Following 
this method, the authors arrived at the following derivatives: — anethole alkamine 



1) Joum. Coll. Enyin., Tokyo 11 (1921), 83. From a special reprint kindly forwarded to us. — ^) Journ. 
pharm. Soc. of Japan 1921, No. 467. As per Chem. Zentralbl. 1921, I. 789. 



152 



Report op Schimmel ^ Co. 1922. 



CH80C»H4CH(NH»)CH(0H)-CHs (m. p. of the acetyl derivative, 111 to 1120), iso- 
safrole alkamine CHjO, : CeHg • CH(IiH,) • CH(OH) • CH, (m. p. 79 % hydrochloride (m. p. 2 tO 
to 215°), W-acetylwosafrole alkamine (m.p.156^), N-benzoylwosafrole alkamine (m. p. 139°), 
N-dimethyli^osafrole alkamine (m. p. 171 to 173°), methyli^oeugehol alkamine (CH30)2: 
C6H,:CH(IiH2)CH(OH)CH8 (m. p. 95 to 96°), hydrochloride (m.p.2220), N-benzoate 
(m. p. 140°), N-methylate (m. p. 90 to 91°). 



Acids, Esters, and Lactones. 

Although the butyric acid fermentation process of the carbohydrates has been in- 
vestigated extensively and has been explained by assuming a condensation process 
like that of acetaldol, or crotOnaldehyde, the experimental ground for this theory was 
still missing. The process was slucidated only by the investigations of C. Neuberg 
and his collaborators. Since Neuberg and Nord^) had shown that in bacterial degrad- 

• 

ation in the sugar series, just as in the alcoholic fermentation of sugar by means 
of yeast, acetaldehyde is formed, Neuberg and B. Arinstein') were now able to per- 
form successfully their investigations on the character of the butyric acid and the 
butylic alcohol fermentations. Their experiments proved that when starch syrup is 
fermented by Bacillus butylicus. Fitz in presence of calcium carbonate, peptone and a 
solution of nutrient salts, 25.16 percent, butyric acid, 7.20 per cent, acetic acid, 1.7 percent, 
butylic alcohol, and 2.23 per cent, ethyl alcohol are the result. ' If under the same con- 
ditions di-sodium sulphite is added, with the object to ''catch off' and eliminate the 
intermediarily-formed acetaldehyde, the result runs as follows: — per cent, butyric 
acid, 20.35 per cent, acetic acid, per cent, butylic alcohol, 13.47 percent, ethyl alcohol, 
and 7.61 percent, acetaldehyde; acetic acid and ethyl alcohol may be regarded as 
dismutation^prodlicts of acetaldehyde. These results prove that the formation of acet- 
aldehyde depends in a certain manner on the true saccharogenic butyric fermentation 
process. The authors found also that a-keto-^'-valerolactone-^^-carboxylic acid, the so- 
called aldol of pyroracemic acid (see below under b), on fermentation with Bac. hutylicus^ 
yields butyric acid in addition to some acetic acid. Pyroracemic acid being considered 
as the intermediary stage of acetaldehyde'), it may be assumed that the degradation 
process of sugar, on butyric fermentation, passes off with pyroracemic acid as inter- 
mediate body, this acid being condensed to the aldol and the latter split up to butyric acid. 
In the authors' opinion, both processes, that of the butyric acid fermentation and of 
the butylalcoholic fission of sugar, can be expressed by the following rough formulas:— 

Butyric acid fermentation of sugar: 

a) CeHiaOe = 2 CH, • CO • COOH + 4 H 

h) 2 CH,- CO COOH = CH8C(0H)C00H 



c) CgHsOe 



CH,- CO COOH 
= 2C08 + C4H8O2. 



Butylic alcohol fission of sugar: 

a) CeHwOe = 2CH«C0C00H + 4H 

h) 2CH8COCOOH = CH8C(0H)C00H 

CH,. CO COOH 
c) CeHaOe + 4H = 2C0, + H2O + C4H10O. 



^) Biochem. Ztgchr. 96 (1919), 133. Cf. Bericht (Germ, ed.) 1920, 140. — ') Biochem. ZtscJir. 117 (1921V 
269. As per a special reprint kindly forwarded to us. — ') Cf. p. 150 of this Beport. 



Notes on scientific research. 153 

Finally the authors were successful in proving a fact of importance from a bio- 
logical stand-point, that when dextrose is fermented with a pure culture of Bac. 
butylicuSj Fitz, caproic acid and higher fatty acids resembling caprylic and caprinic 
acids are formed. 

Of the four pinononic acids obtained from different primary bodies, the acid ob- 
tained by Kerschbaum on oxidising verbenol from verbena oil was known to be 
identical with the acid prepared by Blumann and ZeitscheU) from the autoxidation 
products of pinene (verbenol and verbenone). E. ^romni and R.-l^lein*) now established 
the identity of these two acids with the degradation-product obtained by Fromm and 
Autin*^) from olibanol (of frankincense oil). Kerschbaum's pinononic acid semicarbazone 
(from verbenone), when mixed with the semicarbazone of the acid from olibanol, 
showed no depression of the melting point. In order to test the behaviour of the 
fourth specimen of thie acid, which had been obtained by Wagner and Ershtchikovski*) 
by oxidising pinene with permanganate, Fromm and Klein oxidised pure pinene (b. p. 156 
to 158^; digo 0.8683), from French turpentine oil, with permanganate according to the 
directions given. However, instead of the pinononic acid as expected they obtained 
a pinononic acid contaminated by a small quantity of an acid of the m. p. 100^. They 
are, therefore, of opinion that the acid obtained by Wagner and ErshtchikovsHi is 
due to some impurity in their pinene, preferably to the autoxid^^ion-products con- 
taining verbenol and verbenone. For the reason of cleartng up this question the 
authors started some experiments on olibanol, without, however, arriving at the result 
desired. (Cf. also p. 36 of this Bej^ort.) 

An extensive publication by 0. Aschan on pinabietinic acid, which we dealt with ^) 
following an abstract from the Swedish, has now appeared in lAehig's Annalen% The 
crude material serving for the preparation of the acid was a pine oil called in Sweden 
Tallolja. This pine oil results on evaporating the "black lye" (Schtvarzlauge) of the 
manufacture of sulphate cellulose and treating the soap obtained therefrom with suf- 
phiiric acid or acid sodium sulphate. The product is a darH, thick oil, soluble in 
sodium Carbonate, which t>y distillation with superheated steam can be separated into 
readily and difficultly volatile fatty and resinous acids. It was from such a distillate 
that Aschan obtained pinabietinic acid. 

By catalytic hydrogeriation with hydrogen in xylene solution, K. W. Rosenmund 
and F. Heise') obtained from benzyl benzoate and benzhydryl henzoafe benzoic acid 
(94 per cent.) and hydrocarbons. If increasing quantities of quinoline were added 
(0.2 to 1 mgr. to 5gr. of the esterj the ester saponification was gradually checked. 
With toluene as solvent the reaction did not take. place. 

Benzaldehyde, when treated in the same manner in xylene solution, yielded benzyl 
alcohol (8 per cent.) and preferably dibenzyl ether (52 per cent.). On addition of 
quinoline in rising quantities, the proportion of the ether formed decreased in favour 
of the alcohol. 

From benzyl alcohol and the corresponding acid chlorides H. A. Shonle and 
P. Q. Row®) prepared the following e^f^rs; — Benzyl laurate (m. p. 8.5°, b. p. 209 to 211° 
[11 mm.], dH 0.9457, n24o 1.4812), benzyl myristate (m. p. 20.5o, b. p. 229 to 231° 



1) Cf. Report October 1913, 103. — *) Liebig's Anyialen 425 (1921), 208. — ') Cf. RepoH April 1914, 
63. — *) Cf. Berl. Berichte 29 (1896), 881. — ») Cf. Beticht (Gerrn. ed.) 1920, 149. — •) Liebig'a Annakn 
424 (1921), 117. — ') Berl. Berichte 54 (1921), 2038. — «) Joum. Atneric. chem. Soc. 48 (1921), 361. 



154 Report OF ScHiMMELfiCo. 1922. 

[II mm.], d|^0,9321, nMo.14803), benzyl palmiUte (ra. p. 36.0°, d||0.9136, fi^^ 1.4689), 
benzyl stearate (m.p. 45.8°; nS-|0.9O75,' n=,o 1.4663), benzyl oleate (liquidator, b.p. 237° 
[7 mm.], d^ 0.9330, n^o 1 .4875). 

For the production of large amounts of these benzyl esters it is recommended to 
allow benzyl chloride to react with the anhydrous alkali salt of the fatty acid dissolved 
in an excess ot that acid. 

From by-products resulting from the hydrolysis of proteins S. Kodama^) a series 
of mostly odoriferous esters: — eifty/ n-acetoxi/\soh«coate, b.p. 120 to 121°/20 mm.,, the 
corresponding methyl ester, b.p. 99 to 100°/20mm.[ ethyl a-hemoylisokexoale, b.p. 174 
to 176°/I7 mm.; ethyl a,isovalerjtlisohejL:tiate. b.p. 125 to 128°/10mm. ; ethyl and amyl 
a-chloroisohexoates, b.p. 152 to I53°/10 mm. and 113 to 114°/8 to 10 mm.'). These 
two esters can be converted into the corresponding esters of uohexoic acid by reduction 
with sodium amalgam. "-Acetoxyuohexoic acid phenyliminochlorlde forms prisms which 
when treated with acetic ester and magnesium yield a-ethoxyisohex aldehyde as an oil. 

Bergaptene, — As a continuation of their earlier endeavour") to obtain bergaptene 
and xanthotoxin synthetically, P. Karrer, A, Rudlinger, A. Glattfelder, and L, Waitz*) 
were successful in confirming the constitution suggested for the 2-methyl^'5-hydroxy- 
caumarone-4-acrylic acid described formerly. It remained, therefore, still unanswered 
why the coumarone ring prevents the closing of the coumarin ring. The authors now 
regard the formula suggested by Thoms^) for bergaptene as uncertain. With the 
purpose of elucidating this question the authors undertook to arrive at bergaptene 
from phloroglucinol monomethyl ether lia methoxy-7-acetoxycoumarin. Unfortunately 
it was impossible to add b/omine to the double bond of the coumarin ring without 
simultaneous brominatlon ot the nucleus, so that the experiment had to be broken off. 

Glucosides. 
R. H. Clark and K. B. Gillie") determined the inlicin content in the bark ot various 
British Columbian willows and poplars. The bark was dried for 48 hours at a tem- 
perature of about 110° and digested for three hours with boiling water. The proteins 
were removed by adding lead acetate and the filtrate treated with emulsin. When 
hydrolysis had passed off the amount of the glucose formed was estimated with 
Fehling's solution. Tiie salicin content of the various barks proved to vary considerably; 
in the most cases the spring barks gave higher values than the corresponding autumn barks. 

Salve NutfaaM") 

Sahx Hookenana 

'^ahx fntchenma 

Sahx lasumdra 

S'oiw: purpurea . . . 

Fopulvs tnchocarpa . . . 

Populvg trfnmlovde'i . . . 

>) Jnira ruAu Jiem Vuc 41 <192l)}, 965. As 



. 3.90 per cent. 


4.49 per cent 


■ 9.81 „ „ 


5.09 „ „ 


. 2.80 „ ., 


7.38 „ ., 


■ 2.50 „ „ 


2.51 „ „